JP2015521224A - Polycarbonate copolymers via controlled radical polymerization - Google Patents

Abstract

In one aspect, the invention relates to a copolymer composition comprising polycarbonate and polyacrylate domains, and to a method of preparing the copolymer, wherein the method comprises atom transfer radical polymerization by polycarbonate macroinitiator and vinyl. Reacting with the monomer.

Description

  The present invention relates to a composition comprising a copolymer of polycarbonate and polyacrylate prepared using a controlled radical polymerization technique with suitable optical clarity and scratch resistance.

  Polycarbonate (“PC”) is a synthetic thermoplastic derived from bisphenol and phosgene, or derivatives thereof. Polycarbonate is a linear polyester of carbonic acid and can be formed from dihydroxy compounds and carbonic acid diesters or by transesterification. The polymerization may be an aqueous solution, an interfacial solution, or in a non-aqueous solution.

  Polycarbonate-based materials have high transparency, transparency, heat resistance, ignition resistance, toughness, stability, impact resistance, creep resistance, and mechanical strength, and thus are used in a wide variety of applications. However, polycarbonate-based materials are less resistant to scratching and surface damage than other materials. In particular, polycarbonate based on bisphenol A (“BPA”) has limited scratch resistance. One method of preventing or minimizing scratch damage is to apply a hard coat to an article formed from BPA polycarbonate. There are several disadvantages to such an approach, which requires a separate manufacturing step, which adds additional cost to the article, reduces durability, and manufacturing. Increase in complexity. Another method is to use a scratch resistant material made from a copolymer of BPA and dimethylbisphenolcyclohexane (“DMBPC”). However, these copolymers also have reduced impact resistance and ductility compared to polycarbonate based on BPA. In contrast, polymers such as poly (methyl methacrylate) (“PMMA”) possess high resistance to scratching. However, PMMA does not have suitable structural properties, for example, PMMA does not have the mechanical strength of PC and is brittle to impact forces.

  Scratch resistance is useful for articles whose outer surface may be in physical contact with other objects. For example, routine activities that can scratch an article include sliding on the surface, dropping, and rubbing with other items such as coins or keys when placed in a pocket. Thus, a scratch resistant polymer composition is desirable in articles that require a durable surface finish and appearance. It is often desirable that these articles not only have the scratch resistance obtained by PMMA polymers, but also the strength and transparency of PC polymers.

  PC and PMMA copolymers may be an attractive solution to the aforementioned problems. Unfortunately, despite the great need and effort to combine the desirable properties of these materials PC and PMMA, there have been limited results. For example, the synthesis of polycarbonate-poly (methyl methacrylate) copolymers via sonochemical polymerization of methyl methacrylate (“MMA”) monomer and PC has been reported (see Non-Patent Document 1). In the described method, PC radicals were generated via sonication, whereby free radical polymerization with MMA proceeded. Despite its ability to produce PC-PMMA copolymers, this method does not yield high molecular weight copolymers and free radical polymerization does not provide control of the final structure of the copolymer. E. A. Kang and co-workers (see Non-Patent Document 2) utilize vinyl-terminated PC polymerized with MMA monomer in the presence of azobisisobutyronitrile (“AIBN”) as a free radical initiator. A PC-PMMA copolymer was prepared. The resulting copolymer had a random morphology. Patent Document 1 discloses the synthesis of a graft copolymer of a polycarbonate and an ethylene monomer via free radical polymerization. However, as discussed above, free radical polymerization provides little control of the final structure of the copolymer. U.S. Patent No. 6,057,032 discloses a thermoplastic blend of a copolymer of PC and MMA with naphthyl methacrylate or substituted methacrylate. This blend provides improved scratch resistance while maintaining PC optical properties, but it is a blend and does not have the advantages of a block or graft copolymer. The superiority of the copolymer over the blend in achieving scratch resistance is the It was examined by Okamoto (see Non-Patent Document 3). Okamoto described the preparation of PC-PMMA graft copolymers from PC oligomers and PMMA macromonomers. Okamoto's PC-PMMA copolymer had superior clarity and hardness compared to the PC / PMMA blend.

US Pat. No. 4,310,642 US Patent Application Publication No. 2009/0142537

M. Choi et al., Macromolecular Symposia 2007, 249-250: 350-356. Polymer Engineering & Science 2006, 40: 2374-2384 Okamoto et al., Journal of Applied Polymer Science 2002, 83: 2774-2779.

  It would be desirable to provide a polycarbonate composition with improved scratch resistance that retains the desirable properties of polycarbonate. Specifically, it would be desirable to provide such a polycarbonate that does not require additional coating or processing after molding and retains these properties. The polycarbonate composition may be useful for certain transparent articles, such as optical components, among other applications.

  Thus, it would be beneficial to provide polycarbonate and poly (methyl methacrylate) block and graft copolymers that retain the appropriate impact strength and optical clarity properties.

  In accordance with the objectives of the present invention, as implemented and outlined herein, the present invention, in one aspect, relates to a copolymer composition comprising polycarbonate and polyacrylate domains and to a method of preparing the copolymer. Here, the method includes reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization. In a further aspect, the copolymer is a block copolymer comprising polycarbonate blocks and polyacrylate blocks. In yet a further aspect, the copolymer composition has improved optical properties such as increased transparency, increased transparency, and reduced haze.

In various embodiments, a method for preparing a block copolymer comprising: a) providing a telechelic polycarbonate polymer having terminal hydroxyl groups, wherein the telechelic polycarbonate polymer has a weight of at least about 3,400. Having an average molecular weight and wherein the telechelic polycarbonate polymer comprises aromatic carbonate repeating units; b) the hydroxyl group is represented by the formula
Esterifying by reaction with an acid halide having the structure represented by
Wherein R ¹ is selected from hydrogen, C 1 -C 6 alkyl, — (C 1 -C 6 alkyl) -aryl, and aryl, wherein R ² is C 1 -C 6 alkyl, — (C 1 -C 6 alkyl) -aryl, and A step selected from aryl and wherein each of X ¹ and X ² is a halogen, and c) whereby the formula
Producing a telechelic polycarbonate macroinitiator having a structure represented by:
Wherein PC is a polycarbonate polymer containing aromatic carbonate repeating units, and Z ¹ and Z ² are
A step having
d) reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization, wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and an optional A second initiator, wherein the catalyst is a transition metal or transition metal salt, and wherein the transition metal is Ti, Mo, Re, Fe, Ru, Os, Rh, Co, Ni, Pd , And Cu, wherein the ligand is 2,2′-bipyridine, 4,4′-di (5-nonyl) -2,2′-bipyridine, N, N, N ′, N′-tetra Methylethylenediamine, N-propyl (2-pyridyl) methanimine, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4,4 ′, 4 ″ -tris (5-nonyl) -2,2 ′: 6 ', 2 ″ -terpyridine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N-bis (2-pyridylmethyl) octylamine, 1,1,4,7,10 , 10-hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tris [(2-pyridyl) methyl] amine, 1,4,8,11-tetraaza-1,4,8,11- Tetramethylcyclotetradecane, N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine, diethylenetriamine, triethylenetetramine, N, N-bis (2-pyridylmethyl) amine, tris [2-aminoethyl] Amines, 1,4,8,11-tetraazacyclotetradecane, and N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine And wherein the optional second initiator is selected from a peroxide, hydroperoxide or azo free radical initiator, and e) thereby producing a block copolymer, wherein Wherein the polycarbonate block comprises from about 10% to about 90% by weight block copolymer, wherein the block copolymer has a weight average molecular weight of from about 1,000 to about 70,000. A method is disclosed.

  In a further aspect, disclosed is a copolymer composition, a) a polycarbonate domain, wherein the polycarbonate domain has a weight average molecular weight of at least about 3,400, and wherein The polycarbonate domain is a polycarbonate domain containing aromatic carbonate repeat units, and b) a polyacrylate domain, containing repeat units derived from vinyl monomers, where the polyacrylate domain is a telechelic polycarbonate polymer. In the presence, a copolymer composition comprising a polyacrylate domain, prepared by atom transfer radical polymerization of a vinyl monomer, wherein the polyacrylate domain comprises at least about 2 mol% of the copolymer. In yet a further aspect, the copolymer is a block copolymer comprising polycarbonate blocks and polyacrylate blocks.

In a further aspect, disclosed is a method for preparing a block copolymer comprising: a) providing a telechelic polycarbonate polymer having a terminal hydroxyl group, wherein the telechelic polycarbonate polymer is at least about Having a weight average molecular weight of 3,400, wherein the telechelic polycarbonate polymer comprises aromatic carbonate repeating units; b) the hydroxyl group is represented by a formula of a telechelic polycarbonate polymer;
Esterifying by reaction with an acid halide having the structure represented by
Wherein R ¹ is selected from methyl and ethyl, wherein R ² is selected from methyl and ethyl, and wherein each of X ¹ and X ² is bromo or chloro, and c) thereby ,formula,
Z ¹ -PC-Z ² ,
Producing a telechelic polycarbonate macroinitiator having a structure represented by:
Where PC is a polycarbonate polymer containing aromatic carbonate repeating units, wherein Z ¹ and Z ² are of the formula
A step having
d) reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization, wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and a second Wherein the vinyl monomer is polymethylmethacrylate, wherein the catalyst is a copper salt, wherein the ligand is 2,2′-bipyridine, and wherein The second initiator is azobisisobutyronitrile and e) thereby obtaining a block copolymer, wherein the block copolymer comprises a polycarbonate block and a polymethylmethacrylate block, wherein The polycarbonate block is about 10% by weight Including about 90% by weight of the block copolymer, wherein the block copolymer has a weight average molecular weight of about 10,000 to about 60,000.

In various aspects, disclosed is a method for preparing a block copolymer comprising: a) providing a telechelic polycarbonate polymer having a terminal hydroxyl group, wherein the telechelic polycarbonate polymer is at least Having a weight average molecular weight of about 3,400, wherein the telechelic polycarbonate polymer comprises aromatic carbonate repeating units; b) the hydroxyl group is replaced with the telechelic polycarbonate polymer and 2-bromoiso Esterifying by reaction with butyryl bromide, c) thereby producing the formula:
Z ¹ -PC-Z ² ,
Producing a telechelic polycarbonate macroinitiator having a structure represented by
Where PC is a polycarbonate polymer containing aromatic carbonate repeating units, wherein Z ¹ and Z ² are of the formula
A step comprising:
d) reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization, wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and a second Wherein the vinyl monomer is methyl methacrylate, the catalyst is a copper salt, and the ligand is 2,2′-bipyridine, where the second The initiator is azobisisobutyronitrile, where the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is about 200: 1: 0.05: 0.05. E) a step of obtaining a block copolymer, wherein The copolymer comprises a polycarbonate block and a polymethylmethacrylate block, wherein the polycarbonate block comprises from about 10% to about 90% by weight block copolymer, wherein the block copolymer comprises from about 20,000 to about And a step having a weight average molecular weight of 50,000.

  Further advantages are shown in the description below. It is to be understood that both the foregoing summary and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.

  The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects and together with the description, serve to explain the principles of the invention.

1 shows the overall reaction mechanism of atom transfer radical polymerization (“ATRP”). 2 shows a representative ¹ H-NMR of a representative polycarbonate oligomer used to prepare a representative telechelic polycarbonate macroinitiator. 2 shows a representative ¹ H-NMR of a representative haloester polycarbonate oligomer used to prepare a representative telechelic polycarbonate macroinitiator. ¹ shows a representative ¹ H-NMR of a representative disclosed polycarbonate-PMMA copolymer. 1 shows a transmission electron micrograph of a ruthenium-stained sample of a representative disclosed polycarbonate-PMMA copolymer. 2 shows representative scratch depth data for a representative disclosed polycarbonate-PMMA copolymer compared to a comparative polymer sample. 2 shows a representative ¹ H-NMR of a representative polycarbonate polymer used to prepare a representative telechelic polycarbonate macroinitiator. A representative ¹ H-NMR of 2-bromoisobutyryl bromide is shown. 2 shows a representative ¹ H-NMR of a representative haloester polycarbonate polymer used to prepare a representative telechelic polycarbonate macroinitiator. A representative ¹ H-NMR of a representative haloester polycarbonate polymer after vacuum drying is shown. ¹ shows a representative ¹ H-NMR of a representative disclosed polycarbonate-PMMA copolymer. ¹ shows a representative ¹ H-NMR of a representative disclosed polycarbonate-PMMA copolymer. Figure 2 shows representative scratch depth and width data for a representative disclosed polycarbonate-PMMA copolymer compared to a comparative polymer sample.

  Further advantages of the present invention are set forth in the detailed description portion below, and some will be apparent from the detailed description, or may be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that both the foregoing summary and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.

  Before the compounds, compositions, articles, systems, devices, and / or methods of the present invention are disclosed and described, they may be identified in a particular synthetic method or unless otherwise specified. It should be understood that it is not limited to reagents and can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, exemplary methods and materials are now described.

  All publications mentioned in this specification are herein incorporated by reference to disclose and describe methods and / or materials, to which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such publication by virtue of prior invention. Furthermore, the publication dates indicated herein may differ from the actual publication dates, which may require individual confirmation.

  Aspects of the invention may be described and claimed in a particular legal classification, but this is for convenience only and one skilled in the art will recognize that each aspect of the invention is described in any legal classification, It is understood that it may be claimed. Unless otherwise stated, any method or aspect presented herein is in no way intended to be construed as requiring that the steps be performed in a specific order. Thus, if the method claims are not specifically stated in the claims or the detailed description that the steps should be limited to a particular order, then it is never inferred that the order is inferred. Not intended. This may be an explicit meaning derived from the logic of the sequence of steps or workflow, grammatical construction or punctuation, or any possible explicit interpretation of the number or type of aspects described herein. This applies to principles that are not.

Definitions It is also understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein and in the claims, the term “comprising” includes “consisting of” and “consisting essentially of”. ) "Can be included. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In this specification and in the claims that follow, reference will be made to a number of terms defined herein.

  As used herein and in the appended claims, the singular forms “a, an,” and “the,” do not clearly indicate other in context. As long as it includes multiple references. Thus, for example, reference to “a functional group”, “alkyl”, or “residue” includes a mixture of two or more such functional groups, alkyls, or residues, and the like. Further, for example, reference to a filler includes a mixture of a plurality of fillers.

  All ranges disclosed herein include the endpoints referred to, and can be combined independently (eg, a range of “2 grams to 10 grams” refers to endpoints of 2 grams and 10 grams, As well as all of their intermediate values). The endpoints of the ranges and any values disclosed herein are not limited to the exact ranges or values, and are unclear to the extent that they include values that approximate these ranges and / or values. .

  Ranges can be expressed herein as from “about” (approximately) approximately one particular value and / or to “about (approximately, approximately)” another particular value. When such a range is expressed, another aspect includes from one particular value and / or another particular value. Similarly, when a value is expressed as an approximation, by using the antecedent “about,” it is understood that that particular value forms another aspect. It is further understood that each endpoint of this range is significant both in relation to other endpoints and independent of the other endpoints. It is also understood that there are a number of values disclosed herein, each of which is also disclosed herein as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two specific units is also disclosed. For example, if 10 and 15 are disclosed, 11, 12, 13 and 14 are also disclosed.

  As used herein, the term “optional” or “optionally” means that the events or circumstances described thereafter may or may not occur. And the description is meant to encompass when such an event or circumstance occurs and when it does not occur. For example, the phrase “optionally substituted alkyl” refers to the fact that the alkyl group may be substituted or unsubstituted, and the representation includes substituted alkyl and substituted It is meant to encompass both alkyl groups that are not.

  As used herein, the term “effective amount” refers to an amount sufficient to achieve the desired modification of the physical properties of the composition or material. For example, an “effective amount” of catalyst refers to an amount sufficient to achieve the desired acceleration of the reaction under applicable test conditions. The specific levels as weight percent (wt%) in the composition required as an effective amount are: amount and type of hydrolysis stabilizer, amount and type of polycarbonate polymer composition, amount of impact modifier composition It depends on a variety of factors, including and type, and the end use of the article made with the composition.

As used herein, the term “number average molecular weight” or “Mn” can be used interchangeably and refers to the statistical average molecular weight of all polymer chains in a sample.
Defined by
Here, M _i is the molecular weight of the chain, and N _i is the number of chains of that molecular weight. Mn can be determined for polymers such as polycarbonate polymers or polycarbonate-PMMA copolymers by methods well known to those skilled in the art.

As used herein, the terms “weight average molecular weight” or “Mw” may be used interchangeably and may be represented by the formula:
Defined by
Here, M _i is the molecular weight of the chain, and N _i is the number of chains of that molecular weight. Compared with Mn, Mw takes into account the molecular weight of each chain in determining its contribution to the molecular weight average. Thus, the higher the molecular weight of a given chain, the more that chain contributes to Mw. Mw can be determined for polymers such as polycarbonate polymers or polycarbonate-PMMA copolymers by methods well known to those skilled in the art.

As used herein, “polydispersity index” or “PDI” is used interchangeably to represent the formula:
PDI = Mw / Mn
Defined by

  PDI has a value greater than or equal to 1, but as the polymer chain approaches a uniform chain length, the PDI approaches uniform.

  Disclosed are the components to be used to prepare the compositions of the present invention, and the compositions themselves to be used within the methods disclosed herein. Where these and other materials are disclosed herein and combinations, subsets, interactions, groups, etc. of these materials are disclosed, various individual and collective combinations and interchanges of each of these compounds Although specific references are not expressly disclosed, it is understood that each is specifically assumed and described herein. For example, if a particular compound is disclosed, discussed, and numerous modifications are contemplated that can be made to a number of molecules, including that compound, each of the possible compounds and modifications unless otherwise indicated. And all combinations and permutations are specifically envisioned. Thus, if the classes of molecules A, B and C are disclosed, as well as the classes of molecules D, E and F, and combinations of molecular examples AD, each is not individually mentioned. Each is individually and collectively envisaged, and this is the case for AE, AF, BD, BE, BF, CD, CE, and CF. This means that the combination is considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the AE, BF, and CE subgroups are considered disclosed. This concept applies to all aspects of the present application, including, but not limited to, steps in methods of making and using the compositions of the present invention. Thus, if there are various additional steps that can be performed, each of these additional steps may be performed in conjunction with any particular aspect or combination of aspects of the method of the present invention.

  In this specification and in the appended claims, references to parts by weight of a particular element or component of a composition or article refer to that element or ingredient in that composition or article (in which parts by weight are expressed). By weight relationship between any other elements or components. Thus, for compounds containing 2 parts by weight of component X and 5 parts by weight of component Y, is X and Y present in a weight ratio of 2: 5 and additional components are included in the composition? Whether or not it exists in such a ratio.

  The weight percentage of a component is based on the total weight of the formulation or composition in which the component is included, unless stated to the contrary. For example, if a particular element or component in a composition or article has 8% by weight, it is understood that this percentage is relative to a total composition percentage of 100%.

  Compounds are described using standard nomenclature. For example, any position that is not substituted with any of the indicated groups is understood to have the required bond or its valence filled with hydrogen atoms. A dash ("-") that is not located between two letters or symbols is used to indicate the point of attachment of the substituent. For example, -CHO is attached through carbon of the carbonyl group. Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The term “aliphatic” refers to a linear or branched array of atoms that is not cyclic and has a valence of at least one. An aliphatic group is defined as containing at least one carbon atom. The arrangement of atoms may contain heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen in the skeleton, or may be composed exclusively of carbon and hydrogen. An aliphatic group may be substituted or unsubstituted. Examples of aliphatic groups include, but are not limited to, methyl, ethyl, isopropyl, isobutyl, chloromethyl, hydroxymethyl (—CH ₂ OH), mercaptomethyl (—CH ₂ SH), methoxy, methoxycarbonyl (CH ₃ OCO-), include nitromethyl _{(-CH 2} NO 2), and thiocarbonyl.

  The term “alkyl group” as used herein refers to an array of straight or branched atoms composed exclusively of carbon and hydrogen. This arrangement of atoms may include single, double or triple bonds (typically referred to as alkanes, alkenes or alkynes). An alkyl group may be substituted (ie, one or more hydrogen atoms are replaced) or unsubstituted. Typically, an alkyl group is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl Hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. A “lower alkyl” group is an alkyl group containing from 1 to 6 carbon atoms.

  The term “alkoxy” as used herein is an alkyl group attached through a single terminal ether linkage; that is, an “alkoxy” group may be defined as —OR, where R is as defined above. Alkyl as defined by A “lower alkoxy” group is an alkoxy group containing from 1 to 6 carbon atoms.

  The term “alkenyl group” as used herein is a hydrocarbon group of a structural formula containing at least one carbon-carbon double bond of 2 to 24 carbon atoms. (AB) Asymmetric structures such as C = C (CD) are intended to include both E and Z isomers. This may be presumed herein by a structural formula in which an asymmetric alkene is present, or this may be clearly indicated by the bond symbol C.

  The term “alkynyl group” as used herein is a hydrocarbon group of a structural formula containing at least one carbon-carbon triple bond of 2 to 24 carbon atoms.

The term “aryl group” may be used interchangeably with “aromatic group” and, as used herein, is any carbon-based aromatic group, without limitation. Are benzene, naphthalene and the like. The term “aromatic” also encompasses “heteroaryl groups”, which are defined as aromatic groups having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to nitrogen, oxygen, sulfur and phosphorus. The aryl group may be substituted or unsubstituted. The aryl group may also contain non-aromatic components. For example, a benzyl group is an aryl group that includes a phenyl ring (aromatic component) and a methylene group (non-aromatic component). Exemplary aryl groups include, but are not limited to, phenyl, pyridyl, furanyl, thienyl, naphthyl, biphenyl, 4-trifluoromethylphenyl, 4chloromethylphen-1-yl, and 3-trichloromethylphen- 1- yl _{(3-CCl 3} Ph-), and the like. An aryl group may be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid or alkoxy. Good.

The term “alicyclic” refers to an array of atoms that is cyclic but not aromatic. The alicyclic group may contain heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen in the ring, or may be composed exclusively of carbon and hydrogen. An alicyclic group may contain one or more acyclic components. For example, a cyclohexylmethyl group (C ₆ H ₁₁ CH ₂ ) is an alicyclic functional group containing a cyclohexyl ring (a sequence of atoms that is cyclic but not aromatic) and a methylene group (acyclic component). Examples of alicyclics include, but are not limited to, cyclopropyl, cyclobutyl, 1,1,4,4 tetramethylcyclobutyl, piperidinyl and 2,2,6,6-tetramethylpiperidinyl. .

  The term “cycloalkyl group” as used herein is a non-aromatic carbon-based ring of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. The term “heterocycloalkyl group” is a cycloalkyl group as defined above, wherein at least one of the carbon atoms in the ring is a heteroatom such as, but not limited to, nitrogen, Substituted with oxygen, sulfur or phosphorus.

  The term “aralkyl”, as used herein, is an aryl group having an alkyl, alkynyl, or alkenyl group as described above attached to an aromatic group. An example of an aralkyl group is a benzyl group.

  The term “hydroxyalkyl group” as used herein refers to an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, alkyl halide, as defined above, wherein at least one hydrogen atom is replaced with a hydroxyl group, or A heterocycloalkyl group;

  The term “alkoxyalkyl group” is defined as an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group as described above, wherein at least one hydrogen atom is replaced with an alkoxy group as described above. Is done.

  The term “ester” as used herein is represented by the formula —C (O) OA, where A is an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, as defined above. It may be a cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group.

  The term “carbonate group” as used herein is represented by the formula —OC (O) OR, where R is hydrogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, cyclo, as defined above. It may be an alkyl, halogenated alkyl, or heterocycloalkyl group.

  The term “carboxylic acid” as used herein is represented by the formula —C (O) OH.

  The term “aldehyde” as used herein is represented by the formula —C (O) H.

  The term “keto group” as used herein is represented by the formula —C (O) R, where R is alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl as defined above. Or a heterocycloalkyl group.

  The term “carbonyl group” as used herein is represented by the formula C═O.

The term “ether” as used herein is represented by the formula AOA ¹ where A and A ¹ are independently alkyl, alkyl halide, alkenyl, alkynyl, aryl, heteroaryl, as defined above. It may be a cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group.

The term “sulfooxo group” as used herein is represented by the formula —S (O) ₂ R, —OS (O) ₂ R, or —OS (O) ₂ OR, wherein R is hydrogen Or an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group as described above.

The term “graft copolymer” as used herein refers to a type of branched copolymer in which the polymer backbone and pendant chains are formed from different monomers. This is different from “block copolymers” in which different monomers are present in the backbone. The formula below schematically shows the graft copolymer and the block copolymer, where A and B represent different monomer units.

  Each of the materials disclosed herein is commercially available and / or methods for its production are known to those skilled in the art.

  It is understood that the compositions disclosed herein have specific functions. Disclosed herein are specific structural requirements for performing the disclosed functions, and there are various structures that can accomplish the same function associated with the disclosed structures, and these structures are usually Is understood to achieve the same result.

Copolymer Compositions In accordance with the objectives of the present invention, as realized and outlined herein, the present invention, in one aspect, prepares a copolymer composition comprising polycarbonate and polyacrylate domains, and prepares the copolymer. Wherein the method comprises reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization. In a further aspect, the copolymer is a block copolymer comprising polycarbonate blocks and polyacrylate blocks. In yet a further aspect, the copolymer composition has improved optical properties such as increased transparency, increased transparency, and reduced haze.

In various embodiments, a method for preparing a block copolymer comprising: a) providing a telechelic polycarbonate polymer having terminal hydroxyl groups, wherein the telechelic polycarbonate polymer has a weight of at least about 3,400. Having an average molecular weight and wherein the telechelic polycarbonate polymer comprises aromatic carbonate repeating units; b) the hydroxyl group is represented by the formula
Esterifying by reaction with an acid halide having the structure represented by
Wherein R ¹ is selected from hydrogen, C 1 -C 6 alkyl, — (C 1 -C 6 alkyl) -aryl, and aryl, wherein R ² is C 1 -C 6 alkyl, — (C 1 -C 6 alkyl) -aryl, and A step selected from aryl and wherein each of X ¹ and X ² is a halogen, and c) whereby the formula:
Z ¹ -PC-Z ² ,
To produce a telechelic polycarbonate having a structure represented by
Wherein PC is a polycarbonate polymer containing aromatic carbonate repeating units, and Z ¹ and Z ² are
A step having
d) reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization, wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and an optional A second initiator, wherein the catalyst is a transition metal or transition metal salt, and wherein the transition metal is Ti, Mo, Re, Fe, Ru, Os, Rh, Co, Ni, Pd , And Cu, wherein the ligand is 2,2′-bipyridine, 4,4′-di (5-nonyl) -2,2′-bipyridine, N, N, N ′, N′-tetra Methylethylenediamine, N-propyl (2-pyridyl) methanimine, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4,4 ′, 4 ″ -tris (5-nonyl) -2,2 ′: 6 ', 2 ″ -terpyridine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N-bis (2-pyridylmethyl) octylamine, 1,1,4,7,10 , 10-hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tris [(2-pyridyl) methyl] amine, 1,4,8,11-tetraaza-1,4,8,11- Tetramethylcyclotetradecane, N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine, diethylenetriamine, triethylenetetramine, N, N-bis (2-pyridylmethyl) amine, tris [2-aminoethyl] Amines, 1,4,8,11-tetraazacyclotetradecane, and N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine And wherein the optional second initiator is selected from a peroxide, hydroperoxide or azo free radical initiator, and e) thereby producing a block copolymer, wherein Wherein the polycarbonate block comprises from 10% to 90% by weight of the block copolymer, wherein the block copolymer has a weight average molecular weight of from about 1,000 to about 70,000. Disclosed.

In a further aspect, disclosed is a method for preparing a block copolymer comprising: a) providing a telechelic polycarbonate polymer having a terminal hydroxyl group, wherein the telechelic polycarbonate polymer is at least about Having a weight average molecular weight of 3,400, wherein the telechelic polycarbonate polymer comprises aromatic carbonate repeating units; b) the hydroxyl group is represented by a formula of a telechelic polycarbonate polymer;
Esterifying by reaction with an acid halide having the structure represented by
Wherein R ¹ is selected from methyl and ethyl, wherein R ² is selected from methyl and ethyl, and wherein each of X ¹ and X ² is bromo or chloro, and c) thereby ,formula,
Z ¹ -PC-Z ² ,
Producing a telechelic polycarbonate macroinitiator having a structure represented by:
Where PC is a polycarbonate polymer containing aromatic carbonate repeating units, wherein Z ¹ and Z ² are of the formula
A step having
d) reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization, wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and a second Wherein the vinyl monomer is polymethylmethacrylate, wherein the catalyst is a copper salt, wherein the ligand is 2,2′-bipyridine, and wherein The second initiator is azobisisobutyronitrile and e) thereby obtaining a block copolymer, wherein the block copolymer comprises a polycarbonate block and a polymethylmethacrylate block, wherein The polycarbonate block is about 10% by weight Including about 90% by weight of the block copolymer, wherein the block copolymer has a weight average molecular weight of about 10,000 to about 60,000.

In various aspects, disclosed is a method for preparing a block copolymer comprising: a) providing a telechelic polycarbonate polymer having a terminal hydroxyl group, wherein the telechelic polycarbonate polymer is at least Having a weight average molecular weight of about 3,400, wherein the telechelic polycarbonate polymer comprises aromatic carbonate repeating units; b) the hydroxyl group is replaced with the telechelic polycarbonate polymer and 2-bromoiso Esterifying by reaction with butyryl bromide, c) thereby producing the formula:
Z ¹ -PC-Z ² ,
Producing a telechelic polycarbonate macroinitiator having a structure represented by
Where PC is a polycarbonate polymer containing aromatic carbonate repeating units, wherein Z ¹ and Z ² are of the formula
A step comprising:
d) reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization, wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and a second Wherein the vinyl monomer is methyl methacrylate, the catalyst is a copper salt, and the ligand is 2,2′-bipyridine, where the second The initiator is azobisisobutyronitrile, where the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is about 200: 1: 0.05: 0.05. E) a step of obtaining a block copolymer, wherein The copolymer comprises a polycarbonate block and a polymethylmethacrylate block, wherein the polycarbonate block comprises from about 10% to about 90% by weight block copolymer, wherein the block copolymer comprises from about 20,000 to about And a step having a weight average molecular weight of 50,000.

In a further aspect, R ¹ is selected from methyl, ethyl, propyl, and isopropyl. In a still further aspect, R ¹ is selected from phenyl and naphthyl. In yet a further aspect, R ¹ is methyl. In a still further aspect, R ¹ is ethyl. In yet a further aspect, R ¹ is phenyl. In yet a further aspect, R ¹ is naphthyl.

In a further aspect, X ¹ and X ² are each bromo. In yet a further aspect, X ¹ and X ² are each chloro.

In a further aspect, X ¹ and X ² are each bromo, wherein R ¹ and R ² are each methyl. In yet a further aspect, X ¹ and X ² are each bromo, where R ¹ is hydrogen and R ² is phenyl.

In a further aspect, the telechelic polycarbonate macroinitiator has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of about 500 to about 40,000, wherein the telechelic polycarbonate macroinitiator has a Mw of about 1,000 to about 70,000. Where R ¹ and R ² are independently selected from methyl, ethyl, propyl, and isopropyl, and where X is selected from bromo and chloro. In yet a further aspect, X is bromo. In yet a further aspect, X is chloro. In a still further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 3,000 to about 35,000, and wherein the telechelic polycarbonate macroinitiator is about 6,000 to about 60. Mw of 1,000. In a still further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 10,000 to about 25,000, and wherein the telechelic polycarbonate macroinitiator is about 20,000 to about 50, Mw of 000.

In various embodiments, the telechelic polycarbonate macroinitiator has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of about 500 to about 40,000, wherein the telechelic polycarbonate macroinitiator has a Mw of about 1,000 to about 70,000. And where X is selected from bromo and chloro. In yet a further aspect, X is bromo. In yet a further aspect, X is chloro. In a still further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 3,000 to about 35,000, and wherein the telechelic polycarbonate macroinitiator is about 6,000 to about 60, Mw of 000. In a still further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 10,000 to about 25,000, and wherein the telechelic polycarbonate macroinitiator is about 20,000 to about 50, Mw of 000.

In a further aspect, the telechelic polycarbonate macroinitiator has the following formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of about 500 to about 40,000, and wherein the telechelic polycarbonate macroinitiator has a Mw of about 1,000 to about 70,000. Have. In a still further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 3,000 to about 35,000, and wherein the telechelic polycarbonate macroinitiator is about 6,000 to about 60, Mw of 000. In yet a further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 10,000 to about 25,000, and wherein the telechelic polycarbonate macroinitiator is about 20,000 to about 50 Mw of 1,000.

In a further aspect, the telechelic polycarbonate macroinitiator has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of about 500 to about 40,000, wherein the telechelic polycarbonate macroinitiator has a Mw of about 1,000 to about 70,000. And where X is selected from bromo and chloro. In yet a further aspect, X is bromo. In yet a further aspect, X is chloro. In a still further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 3,000 to about 35,000, and wherein the telechelic polycarbonate macroinitiator is about 6,000 to about 60. Mw of 1,000. In a still further aspect, the telechelic polycarbonate macroinitiator has a Mn of about 10,000 to about 25,000, and wherein the telechelic polycarbonate macroinitiator is about 20,000 to about 50, Mw of 000.

In a further aspect, the telechelic polycarbonate polymer having terminal hydroxyl groups has the formula:
Having the structure indicated by
Here, the telechelic polycarbonate polymer has a Mn of about 2,000 to about 35,000, and wherein the telechelic polycarbonate polymer has a Mw of about 3,400 to about 70,000. In a still further aspect, the telechelic polycarbonate polymer has a Mn of about 3,000 to about 30,000, and wherein the telechelic polycarbonate macroinitiator is about 6,000 to about 60,000. Have Mw. In yet a further aspect, the telechelic polycarbonate polymer has a Mn of about 5,000 to about 25,000, and wherein the telechelic polycarbonate macroinitiator is about 10,000 to about 50,000. Mw.

  In various embodiments, about 1 mol% to about 5 mol% of telechelic polycarbonate polymer is modified by reaction with an acid halide. In a further aspect, about 1 mol% to about 3 mol% of the telechelic polycarbonate polymer is modified by reaction with an acid halide. In yet a further aspect, about 2 mol% to about 3 mol% of telechelic polycarbonate polymer is modified by reaction with an acid halide.

  In a further aspect, reaction with an acid halide results in a telechelic polycarbonate polymer having a halo moiety present at about 1 mol% to about 5 mol%. In a still further aspect, the reaction with an acid halide results in a telechelic polycarbonate polymer having a halo moiety present at about 1 mol% to about 3 mol%. In a still further aspect, the reaction with an acid halide results in a telechelic polycarbonate polymer having a halo moiety present at about 2 mol% to about 3 mol%.

  In a further aspect, the telechelic polycarbonate polymer having terminal hydroxyl groups has a weight average molecular weight of at least 10,000. In a still further aspect, the telechelic polycarbonate polymer having terminal hydroxyl groups has a weight average molecular weight of at least 20,000. In yet a further aspect, the telechelic polycarbonate polymer having terminal hydroxyl groups has a weight average molecular weight of at least 30,000. In a still further aspect, the telechelic polycarbonate polymer having terminal hydroxyl groups has a weight average molecular weight of about 10,000 to about 50,000. In a still further aspect, the telechelic polycarbonate polymer having terminal hydroxyl groups has a weight average molecular weight of about 20,000 to about 50,000. In yet a further aspect, the telechelic polycarbonate polymer having terminal hydroxyl groups has a weight average molecular weight of about 30,000 to about 50,000.

  In a further aspect, the vinyl monomer is selected from methyl methacrylate, acrylate, styrene, and monoethylenically unsaturated nitrile monomers. In a still further aspect, the vinyl monomer is methyl methacrylate. In yet a further aspect, the vinyl monomer is methacrylate. In yet a further aspect, the vinyl monomer is styrene. In a still further aspect, the vinyl monomer is acrylonitrile.

  In various embodiments, the vinyl monomer is methyl methacrylate, and wherein the block copolymer comprises a polycarbonate block and a PMMA block. In a further aspect, the PMMA block is from about 1% to about 90% by weight of the block copolymer composition. In a still further aspect, the PMMA block is about 5% to about 90% by weight of the block copolymer composition. In yet a further aspect, the PMMA block is about 10% to about 90% by weight of the block copolymer composition. In yet a further aspect, the PMMA block is about 5% to about 80%, about 5% to about 70%, about 5% to about 60%, or about 5% by weight of the block copolymer composition. % To about 50% by weight. In a still further aspect, the PMMA block is about 10% to about 80%, about 10% to about 70%, about 10% to about 60%, or about 10% by weight of the block copolymer composition. To about 50% by weight. In yet a further aspect, the PMMA block is about 20% to about 95%, 20% to about 90%, 20% to about 80%, about 20% to about 20% by weight of the block copolymer composition. 70 wt%, about 20 wt% to about 60 wt%, or about 20 wt% to about 50 wt%. In yet a further aspect, the PMMA block is from about 30% to about 95%, 30% to about 90%, 30% to about 80%, about 30% to about 30% by weight of the block copolymer composition. 70 wt%, about 30 wt% to about 60 wt%, or about 30 wt% to about 50 wt%. In a still further aspect, the PMMA block is about 40% to about 95%, 40% to about 90%, 40% to about 80%, about 40% to about 70% by weight of the block copolymer composition. % By weight, about 40% to about 60% by weight, or about 40% to about 50% by weight. In yet a further aspect, the PMMA block is about 1%, about 2%, about 5%, about 7%, about 10%, about 15%, about 20% by weight of the block copolymer composition. About 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70% About 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, or about 98 wt%. In a still further aspect, the PMMA block is about 60% to about 80% by weight of the block copolymer composition. In yet a further aspect, the PMMA block is from about 45% to about 55% by weight of the block copolymer composition.

In a further aspect, the block copolymer has the formula:
Having the structure indicated by
Wherein the block copolymer has a Mn of about 500 to about 40,000, and wherein the block copolymer has a Mw of about 1,000 to about 70,000, wherein R ^3a and Each of R ^3b is independently selected from halogen and hydrogen, where the halogen is the same halogen that is present in the telechelic polycarbonate macroinitiator used in the preparation of the block copolymer. In yet a further aspect, the block copolymer has a Mn of about 3,000 to about 35,000, and wherein the block copolymer has a Mw of about 6,000 to about 60,000. In yet a further aspect, the block copolymer has a Mn of about 10,000 to about 25,000, and wherein the block copolymer has a Mw of about 20,000 to about 50,000.

  In a further aspect, the block copolymer has a weight average molecular weight of about 15,000 to about 50,000. In a still further aspect, the block copolymer has a weight average molecular weight of about 20,000 to about 50,000. In yet a further aspect, the block copolymer has a weight average molecular weight of about 30,000 to about 50,000. In a still further aspect, the block copolymer has a weight average molecular weight of about 40,000 to about 70,000. In yet a further aspect, the block copolymer has a number average molecular weight of about 5,000 to about 30,000. In yet a further aspect, the block copolymer has a number average molecular weight of about 10,000 to about 25,000. In yet a further aspect, the block copolymer has a number average molecular weight of about 15,000 to about 30,000. In yet a further aspect, the block copolymer has a number average molecular weight of about 20,000 to about 30,000.

  In various embodiments, the block copolymer is about 1.7 to about 2.5, about 1.8 to about 2.3, about 1.8 to about 2.1, or about 1.8 to about 1.9. Having a polydispersity of

  In a further aspect, the block copolymer is 500 nanometers (nm) when tested under a load of 40 mN using a trihedral Berkovich diamond indenter having a front surface of about 0.15 micrometers (μm). It has a scratch depth of about 1,000 nm, about 650 nm to about 900 nm, or 700 nm to about 800 nm.

  In a further aspect, the block copolymer is about 10 nm to about 14 nm, about 11 nm to about 13.3 when tested under a load of 40 mN using a trihedral Berkovich diamond indenter with a front of about 0.15 μm. It has a scratch width of 5 nm, or about 11.5 nm to about 13.5 nm.

In a further aspect, the catalyst is Cu or a copper salt. In a still further aspect, the catalyst, CuBr, CuCl, are selected CuCl _2, and the CuBr _2. In yet a further aspect, the catalyst is CuBr. In yet a further aspect, the catalyst is CuCl. In a still further aspect, the catalyst is CuCl _2. In yet a further aspect, the catalyst is CuBr _2.

In a further aspect, the optional second initiator is not present, and the transition metal catalyst is CuBr, _CuCl, is selected from CuCl 2, CuBr _2, and Cu (0). In yet a further aspect, this optional second initiator is absent and the catalyst comprises both Cu (0) and at least one copper salt. In it from a further aspect, the second initiator of this optional is absent, and the catalyst, Cu (0), and CuBr, CuCl, of at least one copper salt selected CuCl _2, and the CuBr ₂ Includes both.

  In a further aspect, the catalytic ligand is 2,2′-bipyridine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, diethylenetriamine, triethylenetetramine, N, N-bis (2-pyridyl). Selected from methyl) amine, tris [2-aminoethyl] amine, 1,4,8,11-tetraazacyclotetradecane, and 1,1,4,7,10,10-hexamethyltriethylenetetramine. In a still further aspect, the catalytic ligand is selected from 2,2'-bipyridine and N, N, N ', N ", N" -pentamethyldiethylenetriamine. In yet a further aspect, the catalytic ligand is 2,2'-bipyridine. In a still further aspect, the catalytic ligand is N, N, N ', N ", N" -pentamethyldiethylenetriamine.

  In various embodiments, an optional second initiator is present. In a further aspect, the second initiator is a peroxide initiator. In a still further aspect, the peroxide initiator is an acyl peroxide, benzoyl peroxide, alkyl peroxide, cumyl peroxide, tributyl peroxide, hydroperoxide, cumyl peroxide, tributyl hydroxy peroxide ( hydroxperoxide), perester, tributyl perbenzoate, alkylsulfonyl peroxide, dialkyl peroxydicarbonate, diperoxyketal, and ketone peroxide. In yet a further aspect, the second initiator is an azo initiator. In a still further aspect, the azo initiator is selected from 1,1'-azobis (cyclohexanecarbonitrile) and 2,2'-azobis (2-methylpropionitrile). In a still further aspect, the azo initiator is 2,2'-azobis (2-methylpropionitrile).

  In a further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, and catalyst ligand is at least about 25: 1: 1: 1. In a still further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, and catalyst ligand is less than about 5000: 1: 100: 200. In yet a further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, and catalyst ligand is about 200: 1: 1: 2.5. In yet a further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, and catalyst ligand is from about 25: 1: 1: 1 to about 5000: 1: 100: 200. In a still further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, and catalyst ligand is from about 25: 1: 1: 1 to about 200: 1: 1: 2.5. In yet a further aspect, the atom transfer radical polymerization reaction further comprises Cu (0), wherein the molar ratio of the vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand, and Cu (0) is: About 200: 1: 1: 2.5: 0.5.

  In a further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is at least about 10: 1: 0.001: 0.001: 0.1. In a still further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is less than about 1000: 1: 0.5: 0.5: 10. In yet a further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is about 200: 1: 0.05: 0.05: 0.1. In yet a further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is about 10: 1: 0.001: 0.001: 0.1 to about 200: 1. : 0.05: 0.05: 0.1. In a still further aspect, the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is about 10: 1: 0.001: 0.001: 0.1 to about 1000: 1: 0.5: 0.5: 10.

  In a further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 25: 1, about 50: 1, about 100: 1, about 125: 1, about 150: 1, about 175: 1, about 200: 1, About 225: 1, about 250: 1, about 275: 1, or about 300: 1. In a still further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 25: 1, about 50: 1, about 100: 1, about 200: 1, about 300: 1, about 400: 1, about 500: 1. About 750: 1, about 1000: 1, about 1500: 1, about 2000: 1, about 2500: 1, about 3000: 1, about 3500: 1, about 4000: 1, about 4500: 1, or about 5000: 1. In yet a further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 25: 1. In yet a further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 50: 1. In a still further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 150: 1. In yet a further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 200: 1. In yet a further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 250: 1. In a still further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 500: 1. In yet a further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 1000: 1. In yet a further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 2000: 1. In a still further aspect, the molar ratio of vinyl monomer to polycarbonate initiator is about 5000: 1.

  In a further aspect, disclosed is a copolymer composition, a) a polycarbonate domain, wherein the polycarbonate domain has a weight average molecular weight of at least about 3,400, and wherein The polycarbonate domain is a polycarbonate domain containing aromatic carbonate repeating units, and b) a polyacrylate domain containing repeating units derived from vinyl monomers, wherein the polyacrylate domains are vinyl monomer atoms. A copolymer composition comprising a polyacrylate domain prepared by transfer radical polymerization in the presence of a telechelic polycarbonate polymer, wherein the polyacrylate domain comprises at least about 2 mol% of the copolymer. Ah . In yet a further aspect, the copolymer is a block copolymer comprising polycarbonate blocks and polyacrylate blocks.

  In a further aspect, the polycarbonate domain aromatic carbonate repeat unit comprises bisphenol A.

  In a further aspect, the polycarbonate domain has a weight average molecular weight of at least 10,000. In a still further aspect, the polycarbonate domain has a weight average molecular weight of at least 20,000. In yet a further aspect, the polycarbonate domain has a weight average molecular weight of at least 30,000. In yet a further aspect, the polycarbonate domain has a weight average molecular weight of about 10,000 to about 50,000. In yet a further aspect, the polycarbonate domain has a weight average molecular weight of about 20,000 to about 50,000. In yet a further aspect, the polycarbonate domain has a weight average molecular weight of about 30,000 to about 50,000.

  In a further aspect, the polyacrylate domain comprises repeat units derived from vinyl monomers selected from methyl methacrylate, acrylate, styrene, and monoethylenically unsaturated nitrile monomers. In a still further aspect, the polyacrylate domain comprises repeat units derived from methyl methacrylate. In yet a further aspect, the polyacrylate domain comprises repeating units derived from methacrylate. In yet a further aspect, the polyacrylate domain comprises repeat units derived from styrene. In yet a further aspect, the polyacrylate domain comprises repeat units derived from acrylonitrile.

  In various embodiments, the polyacrylate domain is PMMA. In a further aspect, the polyacrylate domain is PMMA, wherein PMMA is from about 10% to about 90% by weight of the block copolymer composition. In a still further aspect, the polyacrylate domain is PMMA, wherein PMMA is about 40% to about 80% by weight of the block copolymer composition. In yet a further aspect, the polyacrylate domain is PMMA, wherein PMMA is about 40% to about 90% by weight of the block copolymer composition. In yet a further aspect, the polyacrylate domain is PMMA, wherein PMMA is about 40% to about 60% by weight of the block copolymer composition. In a still further aspect, the polyacrylate domain is PMMA, wherein PMMA is about 60% to about 80% by weight of the block copolymer composition. In yet a further aspect, the polyacrylate domain is PMMA, wherein PMMA is about 45% to about 55% by weight of the block copolymer composition.

  In further embodiments, the copolymer composition is about 1.7 to about 2.5, about 1.8 to about 2.3, about 1.8 to about 2.1, or about 1.8 to about 1.9. Having a polydispersity of

  In a further aspect, the copolymer composition is about 500 nm to about 1000 nm, about 650 nm to about 900 nm when tested under a load of 40 mN using a trihedral Berkovich diamond indenter having a front surface of about 0.15 μm. Or a scratch depth of about 700 nm to about 800 nm.

  In a further aspect, the copolymer composition is about 10 nm to about 14 nm, about 11 nm to about 13 when tested under a load of 40 mN using a trihedral Berkovich diamond indenter having a front surface of about 0.15 μm. .5 nm, or a scratch width of about 11.5 nm to about 13.5 nm.

In various embodiments, the copolymer composition is a block copolymer composition. In a further aspect, the block copolymer composition comprises a polycarbonate block and a polyacrylate block. In a still further aspect, the polycarbonate block is derived from a telechelic polycarbonate macroinitiator. In yet a further aspect, the telechelic polycarbonate macroinitiator has the formula Z ¹ -PC-Z ² below,
Here, PC is a polycarbonate polymer containing aromatic carbonate repeating units,
Where Z ¹ and Z ² are
Wherein R ¹ is selected from hydrogen, C1-C6 alkyl, — (C1-C6 alkyl) -aryl, and aryl, wherein R ² is C1-C6 alkyl, — (C1-C6) Alkyl) -aryl, and aryl, where X is a halogen.

In one aspect, the polycarbonate-polyacrylate copolymers of the present invention can be generally prepared by a synthetic scheme as shown below.

The compounds are shown in general form and the substituents are as described elsewhere in the description of the compounds herein. More specific examples are shown below.

In one aspect, the polycarbonate-polyacrylate copolymers of the present invention can generally be prepared by a synthetic scheme as shown below.

The compounds are shown in general form and the substituents are as described elsewhere in the description of the compounds herein. More specific examples are shown below.

In one aspect, the polycarbonate-polyacrylate copolymers of the present invention can generally be prepared by a synthetic scheme as shown below.

The compounds are shown in general form and the substituents are as described elsewhere in the description of the compounds herein. A more specific example is shown below.

Polycarbonate Polymer Composition As used herein, the term “polycarbonate” includes homopolycarbonates, and copolycarbonates have repetitive structural carbonate units. In one aspect, the polycarbonate is incorporated by reference in its entirety for the specific purpose of disclosing various polycarbonate compositions and methods, for example as described in US Pat. No. 7,786,246. Any polycarbonate material or mixture of materials may be included.

  In one aspect, the polycarbonate may be an aliphatic diol-based polycarbonate as disclosed herein. In another aspect, the polycarbonate may include carbonate units derived from dihydroxy compounds such as, for example, bisphenols, which are different from aliphatic diols.

  In one aspect, non-limiting examples of suitable bisphenol compounds include 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, Bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1, 1-bis (hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy Enyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) isobutene, 1,1-bis (4-hydroxyphenyl) cyclododecane, trans-2 , 3-bis (4-hydroxyphenyl) -2-butene, 2,2-bis (4-hydroxyphenyl) adamantine, (α, α'-bis (4-hydroxyphenyl) toluene, bis (4-hydroxyphenyl) Acetonitrile, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-) Hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bi (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dibromo-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis (5 -Phenoxy-4-hydroxyphenyl) ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis (4-hydroxyphenyl)- -Butanone, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione, ethylene glycol bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide Bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, 9,9-bis (4-hydroxyphenyl) fluorene, 2,7-dihydroxypyrene, 6,6′-dihydroxy-3,3 3 ′, 3′-tetramethylspiro (bis) indane (“spirobiindane bisphenol”), 3,3-bis (4-hydroxyphenyl) phthalide, 2,6-dihydroxydibenzo-p-dioxin, 2,6- Dihydroxythianthrene, 2,7-dihydroxyphenoxatin, 2,7 -Dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, and the like, and at least one of the aforementioned dihydroxy aromatic compounds The combination that is out.

  In another aspect, exemplary bisphenol compounds are 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane. (Hereinafter “bisphenol A” or “BPA”), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4 -Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t- Butylphenyl) propane, 3,3-bis (4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis (4-hydroxyphenyl) Phthalimidine ( "PPPBP"), and 9,9-bis (4-hydroxyphenyl) may include fluorene. Combinations comprising at least one dihydroxy aromatic compound may also be used. In other embodiments, other types of diols may be present in the polycarbonate.

  In yet another aspect, polycarbonates having branched groups may be useful, provided that such branched groups are conditions that do not adversely affect the desired properties of the polycarbonate. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. These branching agents include polyfunctional organic compounds, which contain at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the aforementioned functional groups. . Specific examples include trimellitic acid, trimellitic anhydride, trimellitic acid trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC (1,3,5-tris ((p-hydroxy Phenyl) isopropyl) benzene), tris-phenol PA (4- (4 ′-(1,1-bis (p-hydroxyphenyl) -ethyl) α, α-dimethylbenzyl) phenol), 4-chloroformylphthalic anhydride Products, trimesic acid, and benzophenone tetracarboxylic acid. In one aspect, the branching agent can be added at a level of about 0.05 to about 2.0 weight percent. In yet another embodiment, a mixture comprising linear polycarbonate and branched polycarbonate may be used.

  Polycarbonates, for example isosorbide-based polyester-polycarbonates, are copolymers comprising carbonate units and other types of polymer units (including ester units), and combinations comprising at least one of homopolycarbonates and copolycarbonates. May be included. An exemplary polycarbonate copolymer of this type is polyester carbonate, also known as polyester-polycarbonate. Such copolymers further comprise carbonate units derived from oligomeric ester-containing dihydroxy compounds (also referred to herein as hydroxy end-capped oligomeric acrylate esters).

  In one aspect, the polycarbonate may be manufactured using an interfacial phase transfer process, or melt polymerization. Although the reaction conditions for interfacial polymerization may vary, exemplary processes generally involve dissolving or dispersing the dihydric phenol reactant in aqueous caustic soda or caustic potash and the resulting mixture, for example, chloride. Adding the reaction to a water-immiscible solvent medium such as methylene and the reactants under a controlled pH condition of, for example, about 8 to about 10, for example, of a catalyst such as triethylamine or a phase transfer catalyst salt. Contacting with a carbonate precursor (eg, phosgene) in the presence.

  The polycarbonate compounds and polymers disclosed herein can be prepared in various embodiments by a melt polymerization process. In general, in a melt polymerization process, the polycarbonate is in a molten state in the dihydroxy reactant (ie, isosorbide, aliphatic diol, and / or aliphatic dibasic acid, and any additional dihydroxy compounds) and diaryl carbonate esters, such as , Diphenyl carbonate, or more specifically, in certain embodiments, is prepared by co-reacting an activated carbonate, such as bis (methylsalicyl) carbonate, in the presence of a transesterification catalyst. The reaction can be carried out using typical polymerization equipment, such as one or more continuous stirred reactors (CSTR), plug flow reactors, wire contact flow polymerizers, flow polymerizers, wiped film polymerizers, BANBURY ™ ) It can be carried out in a mixer, a single or twin screw extruder, or a combination of the foregoing. In one aspect, volatile monohydric phenol may be removed from the molten reactants by distillation and the polymer is isolated as a molten residue.

The melt polymerization may comprise a transesterification catalyst comprising a first catalyst, also referred to herein as an alpha catalyst, comprising a metal cation and an anion. In some embodiments, the cation is an alkali or alkaline earth metal, which includes Li, Na, K, Cs, Rb, Mg, Ca, Ba, Sr, or at least one of the foregoing. Includes combinations. This anion includes hydroxide ion (OH ⁻ ), superoxide (O ²⁻ ), thiolate (HS ⁻ ), sulfide (S ²⁻ ), C _1-20 alkoxide, C _6-20 aryloxide, C _{1− 20} carboxylate, phosphoric acid, eg, _biphosphate ion, C _1-20 phosphate, sulfate ion, eg, bisulfate ion, sulfite ion, eg, bisulfite ion and metabisulfite ion, C _1-20 sulfonate ions, carbonates, for example, bicarbonate ions, or a combination comprising at least one of the foregoing. In another embodiment, salts of organic acids that contain both alkaline earth metal ions and alkali metal ions may also be used. Organic acid salts useful as catalysts are exemplified by alkali metal and alkaline earth metal salts of formic acid, acetic acid, stearic acid, and ethylenediaminetetraacetic acid. The catalyst may contain a salt of a non-volatile inorganic acid. “Nonvolatile” means that the compound has no apparent vapor pressure at ambient temperature and pressure. In particular, these compounds are not volatile at the temperatures at which melt polymerization of polycarbonate is normally performed. Non-volatile acid salts are alkali metal salts of phosphites, alkaline earth metal salts of phosphites, alkali metal salts of phosphates, and alkaline earth metal salts of phosphates. Exemplary transesterification catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium formate, sodium formate, potassium formate, cesium formate, Lithium acetate, sodium acetate, potassium acetate, lithium carbonate, sodium carbonate, potassium carbonate, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium phenoxide, sodium phenoxide, potassium phenoxide , Sodium sulfate, potassium sulfate, NaH ₂ PO ₃ , NaH ₂ PO ₄ , Na ₂ H ₂ PO ₃ , KH ₂ PO ₄ , CsH ₂ PO ₄ , Cs ₂ H ₂ PO ₄ , Na ₂ SO ₃ , Na ₂ S ₂ O ₅ , sodium mesylate, potassium mesylate, sodium tosylate, potassium tosylate, ethylenediaminetetraacetate disodium magnesium (EDTA magnesium disodium salt), or a combination comprising at least one of the foregoing. It is understood that the foregoing list is exemplary and should not be considered limiting. In one aspect, the transesterification catalyst is an alpha catalyst that includes an alkali or alkaline earth salt. In exemplary embodiments, the transesterification catalyst comprises sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, NaH ₂ PO ₄ , or at least one of the foregoing. Includes combinations.

  The amount of alpha catalyst may vary greatly according to the conditions of melt polymerization and may be from about 0.001 μmol to about 500 μmol. In some embodiments, the amount of alpha catalyst is about 0.01 to about 20 μmol, specifically about 0.1 μmol to about 10 μmol, per mole of aliphatic diol and any other dihydroxy compound present in the melt polymerization, More specifically, it may be about 0.5 to about 9 μmol, and more specifically about 1 to about 7 μmol.

In another aspect, a second transesterification catalyst, also referred to herein as a beta catalyst, may optionally be included in the melt polymerization process, provided that such second transesterification catalyst is used. Is that the inclusion does not adversely affect the desirable properties of the polycarbonate. Exemplary transesterification catalysts may further include a combination of phase transfer catalysts of formula (R ³ ) ₄ Q ⁺ X above, wherein each R ³ is the same or different and C _{1 A -10} alkyl group, Q is a nitrogen atom or a phosphorus atom, and X is a halogen atom, a C _1-8 alkoxy group or a C _6-18 aryloxy group. Exemplary phase transfer catalyst salts include, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NX, [CH ₃ (CH ₂ ) ₃ ] ₄ PX, [CH ₃ (CH ₂ ) ₅ ] ₄ NX, [CH ₃ (CH ₂ ) ₆ ] ₄ NX, [CH ₃ (CH ₂ ) ₄ ] ₄ NX, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NX, and CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NX Wherein X is a C ⁻ , Br ⁻ , C _1-8 alkoxy group or a C _6-18 aryloxy group. Examples of such transesterification catalysts include tetrabutylammonium hydroxide, methyltributylammonium hydroxide, tetrabutylammonium acetate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium phenolate, or at least one of the foregoing. Combinations including species are mentioned. Other melt transesterification catalysts include alkaline earth metal salts or alkali metal salts. In various embodiments where a beta catalyst is desired, the beta catalyst is a mole of 10 or less, specifically 5 or less, more specifically 1 or less, and more specifically 0.5 or less, relative to the alpha catalyst. May be present in ratio. In another aspect, the melt polymerization reaction disclosed herein uses only alpha catalyst as described herein above and is substantially free of beta catalyst. As defined herein, “substantially free and substantially free” can mean when the beta catalyst is excluded from the melt polymerization reaction. In one aspect, the beta catalyst is less than about 10 ppm, specifically less than 1 ppm, more specifically less than about 0.1 ppm, more specifically based on the total weight of all components used in the melt polymerization reaction. It is present in an amount of about 0.01 ppm or less, and more specifically about 0.001 ppm or less.

In one aspect, an end-capping agent (referred to as a chain terminator) may be used to limit the rate of molecular weight increase as needed, and thus control the molecular weight in the polycarbonate. Exemplary chain terminators include certain monophenolic compounds (ie, phenyl compounds having a single free hydroxy group), monocarboxylic acid chlorides, and / or monochloroformates. Phenolic chain stoppers are, phenol and C ₁ -C ₂₂ alkyl-substituted phenols, e.g., p- cumyl - phenol, resorcinol monobenzoate and p- and tertiary, - butylphenol, cresol, and monoethers of diphenols, such as, p -Illustrated by methoxyphenol. Specific mention may be made of alkyl-substituted phenols having branched alkyl substituents having 8 to 9 carbon atoms. Commercial polycarbonate polymers are generally prepared with endblockers, but such polycarbonate polymers may be used in preparing the copolymer compositions of the present invention. Alternatively, the preparation of polycarbonate polymers for use in the present invention can minimize or eliminate the use of such endblockers, thereby maximizing the presence of available hydroxyl (—OH) groups. .

  In various embodiments, the end group can be derived from a carbonyl source (ie, a diaryl carbonate), monomer ratio selection, incomplete polymerization and chain scission, and any added endblocking groups and It may contain derivatizable functional groups such as groups or carboxylic acid groups. This is because a commercially available polycarbonate polymer usually contains a structural unit derived from diaryl carbonate, and the structural unit may be a terminal group. In a further embodiment, the end group is derived from activated carbonate. These end groups are appropriately substituted alkyl esters of activated carbonates and ends of the polycarbonate polymer chain under conditions where the hydroxy groups react with the ester carbonates of the activated carbonate rather than with the carbonate carbonyls of the activated carbonate. Can be derived from a transesterification reaction with a hydroxy group in In this way, substructures derived from structural units or activated carbonates derived from ester-containing compounds and present in the melt polymerization reaction can form ester end groups. However, such derivatization of the end groups may be omitted if desired in the preparation of the polycarbonate polymer of the present invention to maximize the presence of hydroxyl end groups in the polycarbonate polymer.

  In a further aspect, the hydroxyl (—OH) end groups can be varied and optimized in the polycarbonate polymer used in the copolymer composition of the present invention. For example, in standard commercial processes, excess DPC is typically used in reactions that prepare polycarbonates containing diphenyl carbonate (“DPC”) and bisphenol A. Alternatively, polycarbonates prepared for use in the polymer composition of the present invention may be prepared in a reaction in which a low ratio of DPC: BPA is used, which results in an increase in hydroxyl end groups. Increasing the relative number of hydroxyl end groups per polycarbonate chain can be advantageous for the preparation of the copolymers of the invention. The desired polycarbonate with the appropriate hydroxyl (—OH) end groups is activated using the method described in US Pat. No. 7,482,423, incorporated herein by reference in its entirety. It may be prepared by using carbonate.

  In one aspect, the melt polymerization reaction can be performed by subjecting the reaction mixture to a series of temperature-pressure-time protocols. In some embodiments, this involves gradually increasing the reaction temperature in stages, while gradually decreasing the pressure in stages. In one aspect, this pressure is several steps from about atmospheric pressure at the beginning of the reaction to about 1 millibar (100 Pa) or less toward the end of the reaction, or in another aspect, up to 0.1 millibar (10 Pa) or less. To lower. The temperature may change stepwise starting at a temperature approximately at the melting temperature of the reaction mixture and subsequently raised to the final temperature. In one aspect, the reaction mixture is heated from room temperature to about 150 ° C. In such embodiments, the polymerization reaction is initiated at a temperature of about 150 ° C to about 220 ° C. In another aspect, the polymerization temperature may be up to about 220 ° C. In other embodiments, the polymerization reaction is then raised to about 250 ° C., and then further raised to a temperature of about 320 ° C., and all partial ranges therebetween, as needed. Good. In one aspect, the total reaction time may be from about 30 minutes to about 200 minutes, and may be in all partial ranges therebetween. This procedure generally ensures that the reactants react to obtain a polycarbonate having the desired molecular weight, glass transition temperature, and physical properties. This reaction proceeds to build a polycarbonate chain with the formation of phenol or ester-substituted alcohol by-products, such as methyl salicylate. In one aspect, efficient removal of by-products can be achieved by various techniques such as reducing the pressure. In general, the pressure starts relatively high at the beginning of the reaction, gradually decreases throughout the reaction, and the temperature increases throughout the reaction.

  In one aspect, the progress of the reaction may be monitored by measuring the melt viscosity or weight average molecular weight of the reaction mixture using techniques known in the art such as gel permeation chromatography. These properties may be measured by taking separate samples or measured online. After the desired melt viscosity and / or molecular weight is achieved, the final polycarbonate product may be separated from the reactor in solid or molten form. The methods of making aliphatic homopolycarbonates and aliphatic-aromatic copolycarbonates as described in the previous section may be performed in a batch process or a continuous process, and the processes disclosed herein are preferably One skilled in the art will appreciate that this is done in a solvent-free manner. The reactor selected should ideally be self-cleaning and “hot spots” should be minimized. However, a vent type extruder similar to a commercially available one may be used.

  In addition to polycarbonate, the thermoplastic composition may include various additives normally incorporated into this type of resin composition, although this additive is less detrimental to the desired properties of the thermoplastic composition. It is a condition that is selected so as not to have a significant influence. Combinations of additives may be used. Such additives may be mixed at an appropriate time during the mixing of the ingredients to form the composition.

  In other embodiments, the polycarbonate composition comprises one or more antioxidants, such as phosphorus-containing stabilizers and hindered phenols, flame retardants, heat stabilizers, light stabilizers, UV absorbing additives, plasticizers. , Lubricants, mold release agents, antistatic agents, colorants (eg, pigments and / or dyes), or combinations thereof.

  The compositions of the present invention can be blended with the aforementioned ingredients by a variety of methods including intimately mixing the material and any additional additives desired in the formulation. Melt processing is generally preferred due to the availability of melt blending equipment in commercial polymer processing facilities. Illustrative examples of equipment used in such melt processing methods include co-directional and cross-directional extruders, single screw extruders, co-kneaders, disc-pack processors. ) And various other types of extrusion equipment. The temperature of the melt in the process of the present invention is preferably minimized to avoid excessive decomposition of the resin. While it is often desirable to maintain a melting temperature of about 230 ° C. to about 350 ° C. in the molten resin composition, higher temperatures may be used. However, it is a condition that the residence time of the resin in the processing apparatus is kept short. In some embodiments, the melt processed composition exits a processing device such as an extruder through a small exit hole in the die. The resulting strand of molten resin is cooled by passing the strand through a water bath. The cooled chain may be chopped into small pellets for packaging and further handling.

  Thermoplastic compositions containing blended polycarbonate compositions may be made by a variety of methods. For example, powdered polycarbonate, other polymer (if present), and / or any other ingredients are first blended with a filler as needed in a HENSSCHEL-Mixer® high speed mixer. . This blend may also be achieved by other low shear processes including, but not limited to, hand mixing. This blend is then fed via a hopper to the throat of a twin screw extruder. Alternatively, at least one component may be incorporated into the composition by feeding directly to the throat of the extruder and / or feeding downstream through a side stuffer. The additive may be blended into a masterbatch containing the desired polymer resin and fed to the extruder. The extruder is generally operated at a temperature higher than that required to cause the composition to flow. The extrudate is rapidly quenched and pelletized in a water bath. The pellets so prepared may have a length of a quarter inch or less as needed when the extrudate is cut. Such pellets may be used for subsequent molding, cutting or forming.

  “Controlled / living” radical polymerization (CRP) has become one of the solid and powerful technologies for polymer synthesis over the past decade. CRP may be achieved by creating a dynamic equilibrium between the dormant species and the growing radical through a reversible deactivation or chain transfer procedure. This goal includes stable free radical polymerization (SFRP), primarily nitrogen oxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), and Te, Sb, and Bi. It can be achieved by several recently developed controlled polymerization techniques including mediated polymerization, reversible chain transfer catalyzed polymerization.

  Matyjaszewski and co-workers have developed a basic four-component atom transfer radical polymerization (ATRP) process for molecules with an initiator, in this case a transferable atom or group that is fully incorporated into the final product. Addition or in situ formation, transition metals and ligands (participating in reversible redox reactions with additive initiators or dormant polymers to form active species and copolymerize monomers polymerizable to radicals, partially A number of improvements to the basic ATRP process, and a number of patents and patent applications by the same applicant, US Pat. No. 5,763,546; No. 5,807,937; No. 5,789,487; No. 5,945,491; No. 6,111,02 No. 6,121,371; No. 6,124,411; No. 6,162,882; No. 6,624,262; No. 6,407,187; No. 6 No. 6,538,091; No. 6,541,580; No. 6,624,262; No. 6,627,314; No. 6,759,491 No. 6,790,919; No. 6,887,962; No. 7,019,082; No. 7,049,373; No. 7,064,166; No. 125,938; No. 7,157,530; No. 7,332,550 and US Patent Application Publication No. 09 / 534,827; PCT / US04 / 09905; PCT / US05 / 007264; PCT / US05 / 007265; PCT / US06 / No. 3152; PCT / US2006 / 048656 and No. PCT / US08 / 64710 Pat discloses the (all of which are incorporated herein by reference).

ATRP is one of the most efficient CRP methods for the preparation of pure segmented copolymers. Because it does not require the addition of a radical initiator to continuously form new polymer chains, thereby providing a predetermined degree of polymerization, a low molecular weight distribution (M _w / M _n ), incorporation of a wide range of functional monomers, And synthesis of novel multi-segmented copolymers with controllable macromolecular structure presentation is possible under mild reaction conditions. ATRP generally uses alkyl halides or (pseudo) halides as initiators (RX) or dormant polymer chain ends (Pn-X), and partially soluble transition metals that can undergo redox reactions. It is necessary to form or add a complex (eg Cu, Fe or Ru) as a catalyst. As shown in Scheme 1, ATRP encompasses equivalent cleavage of Pn-X bonds by transition metal complexes ^_(M t n -Y / ligand) (rate constant _k a), followed by growth (rate constant _k p), and reversible deactivation of the growing chain radical (Pn ^·) (rate constant k _d) takes place (due to the movement of repetitive halogen or pseudo halogen atom from the transition metal complex and the transition metal complex). This polymer grows by the insertion of monomers present in the reaction medium between the Pn- and -X bonds.

Articles In various aspects, the disclosed copolymer compositions of the present invention are suitable for use in molding articles. In a further aspect, the disclosed copolymer composition of the present invention is suitable for use in film casting to provide an article. In yet a further aspect, the disclosed copolymer composition of the present invention is suitable for use in a coating process to provide an article.

  In a further aspect, the disclosed method of preparing a copolymer may be used to prepare a copolymer used in the molding of an article. In yet a further aspect, the disclosed method of preparing a copolymer may be used to prepare a copolymer for use in film casting to provide an article. In yet a further aspect, the disclosed method of preparing a copolymer may be used to prepare a copolymer for use in a coating process to provide an article.

  The molded product may be compression molded, injection molded, blow molded, injection blow molded, or extruded. The article may also be a solid sheet, an extruded multilayer sheet, a cast film, or an extruded film. The article may also be a multi-layer article in which the capping layer or outer layer is made of a copolymer composition that utilizes the surface properties of the copolymer composition. Such multilayers include coextruded solid sheets, coextruded laminated sheets, coextruded films, or film casting onto separately molded parts. Alternatively, the multilayer may be made by molding different resins on a film made from the copolymer composition. Examples of such applications include optical lenses or bezels. Multi-layers can be useful for consumer electronics. In a further aspect, a method of manufacturing an article includes melt blending a copolymer composition and additives suitable for manufacturing the article, such as antistatic agents, mold release agents and colorants, and an extruded composition. Forming an article into an article. In a still further aspect, this extrusion step is performed in a single screw or twin screw extruder.

  In a further aspect, an article comprising the disclosed copolymer composition is used in automotive applications. In a still further aspect, the article comprises a computer and office equipment housing, eg, a monitor housing, a portable electronic equipment housing, eg, a mobile phone housing, an electrical connector, a medical instrument, a membrane device, and a luminaire component. , Decorations, household appliances, roofs, greenhouses, solariums, pool enclosures and the like. Other exemplary articles that may be assembled using the disclosed copolymer compositions provided herein include headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp bezels, license plate housings. Body, electronics and telecommunications equipment housing, architectural and construction applications, eg glass, roofing, windows, floors, finishing or processing of decorative windows, processing glass covers for display items such as photographs, paintings, posters, optics Lenses, ophthalmic lenses, orthodontic ophthalmic lenses, implantable ophthalmic lenses, wall panels and doors, protected graphics, outdoor and indoor signs, cash dispenser (ATM) housings, housings, panels , Parts, housing, computer housing, desktop computer housing , Portable computer housing, laptop computer housing, palmtop computer housing, monitor housing, printer housing, keyboard, fax machine housing, copier housing, phone housing, mobile phone housing, radio transmission Applications include machine housings, radio receiver housings, lighting fixtures, lighting devices, network interface equipment housings, and the like. In yet a further aspect, articles used in automotive applications include: instrument panel, overhead console, interior, central console, headlamp bezel, headlamp, taillamp, taillamp housing, taillamp bezel, license plate housing, steering Choose from wheels, radio speaker grilles, mirror housings, grill opening reinforcements, steps, hatch covers, knobs, buttons and levers. Additional manufacturing operations such as, but not limited to, molding, in-mold decoration, baking in a coating furnace, lamination and / or thermoforming may be performed on the article.

  In various aspects, an article comprising the disclosed copolymer composition is suitable for use in applications such as a transparent keypad for a mobile phone, where the user is at a low temperature (below 100 ° C). ) Requires the ability to mold these films, and further requires improved punch ductility and chemical resistance. Other typical such articles are the front of automotive equipment, automotive interiors, telecommunications and appliances. In a further embodiment, where the article is a film, it may further include visual effect pigments (eg, coated Al and glass flakes). In yet a further aspect, the article is a film comprising the disclosed copolymer composition and may be used in direct film applications, but also in processes such as IMD (in-mold decoration) However, it may be used. In yet a further aspect, articles comprising the disclosed copolymer compositions are used in lighting applications including lenses for automotive headlamps, lenses for covers and other optical devices, and transparent films and sheets. The article also includes a wide variety of molded products such as medical instruments, radio and TV bezels, cell phone keypads, notebook computer housings and keys, optical display films, automotive parts, and other electrical products, It can also be used in consumer goods.

  Also provided are cut molded, molded or molded articles comprising a thermoplastic composition. The thermoplastic composition may be formed into useful molded articles by various methods such as injection molding, extrusion molding, rotational molding, blow molding and thermoforming. Alternatively, film casting and coating may be used to form the article as required for efficient and useful manufacture of the desired article. The foregoing methods may be used, as appropriate, for example, for example, in computer and office equipment housings, such as monitor housings, portable electronics housings, such as mobile phone housings, electrical connectors, medical instruments, membrane devices, and Lighting fixture components, decorations, household appliances, roofs, greenhouses, solariums, pool enclosures, headlamp bezels, headlamps, tail lamps, tail lamp housings, tail tamp bezels, license plate housings, electronics Equipment and telecommunications equipment enclosures, architectural and construction applications, eg glass, roofs, windows, floors, finishing or processing of decorative windows, processing of display items such as photographs, paintings, posters, glass covers, optical lenses, ophthalmology Lenses, corrective ophthalmic lenses, implantable ophthalmic lenses , Wall panels and doors, protected graphics, outdoor and indoor signs, automated teller machine (ATM) housings, housings, panels, parts, housings, computer housings, desktop computer housings, portable computers Housing, laptop computer housing, palmtop computer housing, monitor housing, printer housing, keyboard, fax machine housing, copier housing, telephone housing, mobile phone housing, radio transmitter housing , Radio receiver housing, lighting fixtures, lighting equipment, network interface equipment housing, instrument panel, overhead console, interior parts, central console, headlamp base , Head lamp, tail lamp, tail lamp housing, tail lamp bezel, license plate housing, steering wheel, radio speaker grill, mirror housing, grill opening reinforcement, steps, hatch covers, knobs, buttons and levers Or you may manufacture. Alternatively, film casting and coating may be used to form the article as necessary for efficient and useful manufacture of the desired article.

  Without further effort, one of ordinary skill in the art would be able to utilize the invention using the description herein. The following examples are included to provide additional guidance for those of ordinary skill in the art to practice the claimed invention. The examples provided are merely representative of the work and contribute to the teaching of the present invention. Accordingly, these examples do not in any way limit the invention.

  Aspects of the invention may be described and claimed in certain legal classifications, such as system legal classifications, but this is merely for convenience and those skilled in the art will recognize that each aspect of the invention is optional. Understand that it can be described and claimed in legal classification. Unless expressly stated otherwise, any method and aspect presented herein is in no way intended to be construed as requiring that the steps be performed in a specific order. Thus, if a method claim does not specifically state in the claims or the specification that the steps are limited to a particular order, then some order is assumed. Never intended. This also applies to the possible non-explicit principles regarding interpretation, including the plain meaning derived from the logic, grammar construction or punctuation regarding the flow of steps or the flow of operations, or the aspects described herein. The number or type of problems.

  Throughout this application various publications are cited. The disclosures of those publications in their entirety are hereby incorporated by reference into this application and describe the situation in the field to which they belong in more detail. The references disclosed are also individually and specifically incorporated by reference herein for their contents, which are referred to by the text on which they depend. Nothing in this specification should be construed as an admission that the invention is not entitled to antedate such publication by virtue of prior inventions. In addition, the publication dates indicated herein may differ from the actual publication dates, which may require individual confirmation.

  The following examples are presented to provide those skilled in the art with a complete disclosure and description of how the methods, devices and systems disclosed and claimed herein are made and evaluated. And is intended to be purely exemplary and not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (eg, amounts, temperature, etc.) but some error and deviation should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is C or normal temperature, and pressure is at or near atmospheric.

The materials described in Table 1 were used to prepare the compositions described herein.

  Reaction conditions such as concentration of components, desired solvent, solvent mixture, temperature, pressure, and other reaction ranges and conditions that can be used to optimize the purity and yield of the products obtained from the described process There are numerous modifications and combinations. Only reasonable and routine experimentation is required to optimize such working conditions.

Standard Test Methods Samples were also tested for scratch resistance using a Nanoindenter ™ G200 (Agilent Technology, Santa Clara, Calif.). The material surface was scratched using a three-sided Berkovich diamond indenter (front, approximately 0.15 μm diameter). A typical scratch experiment was performed in four stages: original profile, scratch segment, residual profile, and cross-sectional profile. The test parameters used in this study are shown in Table 2 below. Data obtained using the scratch resistance test method are shown in Tables 5 and 8.

  Also, transparency, haze and transparency properties of films prepared from the copolymers disclosed herein are described in ASTM International Standard No. D1003-00 “Standard Test Method for Haze and Luminous Transient of Transparent Plastics” (July 2000). Measured with a 2.5 mm thick molded plate in accordance with (publication). Measurements were made using a BYK Gardner Hazeguard Dial. In principle, a percentage of light transmission above 85% is considered “transparent”. The copolymers disclosed herein had the following properties, transparency was 87-90%, haze was 9-14%, and transparency was 98-99% ( As measured by ASTM-D1003).

Preparation of polycarbonate macroinitiator A polycarbonate macroinitiator was prepared from PC1, bisphenol A polycarbonate listed in Table 1. Generally, PC1 has a Mw of about 10,000 and a Mn of about 5,000. A representative ¹ H-NMR trace of PC1 is shown in FIG. In this experiment, PC1 had a Mw of 9,740 and a Mn of 5,055.

  Briefly, 2-bromoisobutyryl bromide (1.64 g, 7.2 mmol) was dissolved in THF (3 mL). PC1 (20 g, 2.0 mmol) was dissolved in THF (20 mL) with heating at 60 ° C. The 2-bromoisobutyryl bromide solution was added dropwise to the PC1 solution, then 0.56 g of pyridine (in 4 mL of THF) was added dropwise, and the reaction mixture was allowed to react at 60 ° C. for about 24 hours. The contents were then cooled. The reaction mixture was precipitated into methanol, filtered and washed several times with methanol to remove untreated material. The isolated polycarbonate macroinitiator is then dried at 50 ° C. under reduced pressure to obtain a polycarbonate macroinitiator, referred to hereinafter as “PC1-Min”.

¹ H-NMR analysis was performed on PC1-Min and the data is shown in FIG. Isolated PC1-Min had slightly reduced Mw and Mn (8,843 and 3,483, respectively) compared to PC1 prior to reaction with 2-bromoisobutyryl bromide .

Alternatively, the polycarbonate macroinitiator was prepared from PC2, the polycarbonate polymer listed in Table 1. PC2 has a Mw of about 22,500 to about 33,000 and a Mn of about 11,700 to about 15,700. A representative ¹ H-NMR trace of PC1 is shown in FIG. In this experiment, PC2 had a Mw of 33,586, a Mn of 15,756, and a ppm (OH) of 3363.71. The phenolic hydroxyl group is quantified by using ³¹ P-NMR, and the data is used to determine “ppm (OH)”, where 1 ppm indicates 1 mg of phenolic hydroxyl group per kg of the polycarbonate polymer.

Briefly, 2-bromoisobutyryl bromide (4.00 g, 17.6 mmol) was dissolved in THF (15 mL). A representative ¹ H-NMR trace of 2-bromoisobutyryl bromide is shown in FIG. PC2 (20 g, 0.5 mmol) was dissolved in THF (200 mL) with heating at 60 ° C. The 2-bromoisobutyryl bromide solution was added dropwise to the PC2 solution, then 1.50 g of pyridine (in 10 mL of THF) was added dropwise and the reaction mixture was allowed to react at 60 ° C. for about 21 hours. The contents were then cooled and the reaction mixture was precipitated in methanol, filtered and washed several times with methanol to remove unreacted material. The isolated polycarbonate macroinitiator is then dried at about 50 ° C. under reduced pressure for about 5-6 hours to obtain a polycarbonate macroinitiator, hereinafter referred to as “PC2-Min”. Call. The bromo group content in a typical batch of polycarbonate macroinitiator prepared by this method was about 2.7 mol%.

¹ H-NMR analysis was performed on PC2-Min before vacuum drying, and the data is shown in FIG. 9, and ¹ H-NMR analysis was performed on PC2-Min after vacuum drying, and the data was As shown in FIG. Isolated PC2-Min had slightly reduced Mw and Mn (27,271 and 14,656, respectively) compared to PC2 prior to reaction with 2-bromoisobutyryl bromide. The ppm (OH) of PC2-Min was 1887.94. As expected, this value was reduced compared to the PC2 starting material due to the reaction of 2-bromoisobutyryl bromide with the phenolic hydroxyl group of PC2.

  It should be noted that the polycarbonate polymer used in the preparation of PC2-Min was purified from additives and contaminants prior to use in the above reaction, except as noted below for the APM3 batch. is there. Briefly, polycarbonate pellets were dissolved in dichloromethane and the polycarbonate polymer was precipitated from solution with methanol, thereby obtaining a purified white powder. The precipitated polycarbonate polymer was then dried under reduced pressure at about 50 ° C. for about 5-6 hours to remove residual methanol.

  Mn and Mw were determined using data obtained by standard chromatographic procedures. Briefly, GPC was performed by first dissolving the sample in dichloromethane at a concentration of 1 mg / ml. The sample was then analyzed by GPC using a Polymer Laboratories MiniMIX-C column (Polymer Laboratories, Varian, a division of Amherst, Mass.) With a mobile phase of dichloromethane and a flow rate of 0.3 ml / min. The detection wavelength was 254 nm, Mw results were reported against polystyrene standards, GPEC analysis was also performed, a sample was prepared at 5 mg / ml in THF and 5 ul was HPLC (The flow rate was 1 ml / min.) Gradient separation was applied from 100% methanol to 100% THF over 20 minutes and back to 100% methanol, the column was fitted with GraceSmart RP- C18 (5 μm, 150 mm x 4.6 mm) (Mandel Scientific, Guelph, Ontario, Canada) Detection was by ELSD and DAD-UV Peaks were identified by comparison to polymer standards.

Copolymer Batch Representative copolymers were prepared by ATRP using reactants as shown in Tables 2 and 5 for copolymer batches prepared using PC1-Min and PC2-Min, respectively. The values obtained in each batch are the amount of each item in grams used in the indicated batch unless otherwise indicated (eg, solvent, anisole or toluene are given in mL). Reaction times and temperatures for the indicated batches were as shown in Tables 2 and 5. Specific notes for each preparation are shown below.

  Briefly, the PC macroinitiator was dissolved in degassed anisole in a nitrogen purged reaction vessel, such as a round bottom flask. The solution was stirred for several minutes and then MMA, catalyst, and ligand were added in the amounts shown in Tables 2 and 5. The solution was stirred for about 10 minutes to form a red-colored Cu-ligand complex. The reaction was then heated at the indicated temperature, eg, in an oil bath for the indicated time (see Tables 2 and 5). In some batches, after the reaction, the reaction mixture was diluted with chloroform and passed through a neutral alumina column to remove residual catalyst. The resulting solution was concentrated and precipitated in excess methanol and then dried at 40 ° C. under reduced pressure until a constant weight was reached.

Batch APM1
Batch APM1 was prepared as described in Table 3. The resulting copolymer was slightly colored (greenish shade). A representative ¹ H-NMR trace of the resulting copolymer is shown in FIG. The PMMA content of the copolymer was estimated to be about 50 mol% from these ¹ H-NMR data. Briefly, the characteristic —OCH ₃ (3H) peak (see FIG. 4) is associated with PMMA and determines the ratio of this peak to the integral signal of polycarbonate aromatic hydrogen (ie, FIG. 4). 8H Ar H peak shown in FIG. The size characteristics of the APM1 copolymer are shown in Table 4 below.
* All component amounts are given as weight (g) except anisole and toluene as volume (mL).

Batch APM2
Batch APM2 was prepared using unwashed macroinitiator as described in Table 3. The resulting copolymer was a dark color. A sample of batch APM2 was analyzed using a transmission electron microscope. Briefly, very thin portions of copolymer samples were prepared using a microtome and several sections were stained with ruthenium tetroxide. Ruthenium tetroxide preferentially dyes the polycarbonate domain of the copolymer but does not dye the PMMA domain of the copolymer. A representative photomicrographic image is shown in FIG. 5 (Panel AC, unstained; Panel DF, stained with ruthenium; magnification is shown below each micrograph). As shown in the image (see panels DF), the polycarbonate (darkly stained) is evenly distributed in the light gray background of PMMA. The uniform dispersion of polycarbonate and PMMA domains suggests the formation of a copolymer that is not just a physical blend of separate polycarbonate and PMMA polymer. While not wishing to be bound by any particular theory, the uniformity of dispersion of the polycarbonate and PMMA domains of the copolymer is important for the transparency observed in films prepared from the disclosed copolymers. The size characteristics of the APM2 copolymer are shown in Table 4 below, and the scratch resistance properties are shown in Table 5 below. The comparative materials shown in Table 5 are as follows. PMMA is a commercially available grade of PMMA with an Mw of 80 kg / mol. DMBPC is a polycarbonate homopolymer prepared via interfacial polymerization at Mw of 60 kg / mol and was prepared for these studies. DMX is a commercial polycarbonate polymer of SABIC-IP. PC145 is a pure polycarbonate resin available in the SABIC-IP company with Mw of 26,200 and 55 kg / mol.

Batch APM3
Batch APM3 was prepared using unwashed macroinitiator as described in Table 6. The molar ratio of MMA: PC2-Min: CuBr: Bpy: Cu (0) in the polymerization reaction was about 50: 1: 1: 2: 0.5. The resulting copolymer was a dark color. In contrast to batch APM4, APM5, and APM6, PC2-Min used in the preparation of APM3 was not subjected to a washing step or vacuum drying either before or after synthesis of PC2-Min (PC2-Min's (See discussion above regarding preparation).
* All component amounts are given as weight (g), where anisole is given as volume (mL).

Batch APM4
Batch APM4 was prepared as described in Table 6 using a washed and dried macroinitiator. The molar ratio of MMA: PC2-Min: CuBr: Bpy: Cu (0) in the polymerization reaction was about 25: 1: 1: 2.5: 0.5. The resulting copolymer was a dark color.

Batch APM5
Batch APM5 was prepared as described in Table 6 using a washed and dried macroinitiator. MMA in the polymerization reaction: PC2-Min: AIBN: Bpy: molar ratio of CuBr ₂ is about 200: 1: 0.1: 0.05: was 0.05. PMMA content was evaluated using ¹ H-NMR as described above for batch APM1. The apparent MMA content was about 50 mol%. Further characterization of the molar weight of the resulting copolymer is shown below in Table 7, and nanoindentation data is shown in Table 8 and FIG. The size characteristics of the APM5 copolymer are shown in Table 7, and the data in Table 7 shows the average of two runs with a standard deviation. The scratch resistance characteristics for the copolymer batch are shown in Table 8. The comparative materials in Table 8 are as described above for Table 5.

Batch APM6
Batch APM3 was prepared as described in Table 6 using the washed and dried macroinitiator. The molar ratio of MMA: PC2-Min: CuBr: Bpy: Cu (0) in the polymerization reaction was about 200: 1: 1: 2.5: 0.5. The resulting copolymer was a dark color. The apparent MMA content was about 88 mol% and was determined as described above. Further characterization of the molar weight of the resulting copolymer is shown below in Table 7, and nanoindentation data is shown in Table 8 and FIG. The size characteristics of the APM6 copolymer are shown in Table 7, and the data in Table 7 shows the average of two runs, with a standard deviation. The scratch resistance characteristics for the copolymer batch are shown in Table 8. The comparative materials in Table 8 are as described above for Table 5.

  Shown below are some embodiments of the methods, copolymers, and articles disclosed herein.

Embodiment 1 A method for preparing a block copolymer comprising providing a telechelic polycarbonate polymer having terminal hydroxyl groups, wherein the telechelic polycarbonate polymer has a weight average molecular weight of at least 3,400. And wherein the telechelic polycarbonate polymer comprises aromatic carbonate repeating units;
The hydroxyl group, a telechelic polycarbonate polymer, a formula,
Esterifying by reaction with an acid halide having the structure represented by
Wherein R ¹ is selected from hydrogen, C1-C6 alkyl,-(C1-C6 alkyl) -aryl, and aryl, wherein R ² is C1-C6 alkyl,-(C1-C6 alkyl) -aryl, and A step selected from aryl, wherein X ¹ and X ² are halogen;
Thereby, the formula,
Z ¹ -PC-Z ² ,
Producing a telechelic polycarbonate macroinitiator having a structure represented by:
Wherein PC is a polycarbonate polymer containing aromatic carbonate repeating units, and Z ¹ and Z ² are
A step having
The polycarbonate macroinitiator is reacted with a vinyl monomer by atom transfer radical polymerization,
Wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and an optional second initiator;
Wherein the catalyst is a transition metal or transition metal salt, and wherein the transition metal is selected from Ti, Mo, Re, Fe, Ru, Os, Rh, Co, Ni, Pd, and Cu;
Here, this ligand includes 2,2′-bipyridine, 4,4′-di (5-nonyl) -2,2′-bipyridine, N, N, N ′, N′-tetramethylethylenediamine, N-propyl ( 2-pyridyl) methanimine, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4,4 ′, 4 ″ -tris (5-nonyl) -2,2 ′: 6 ′, 2 ″ -terpyridine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N-bis (2-pyridylmethyl) octylamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine , Tris [2- (dimethylamino) ethyl] amine, tris [(2-pyridyl) methyl] amine, 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane, N, N , N ′, N′-tetrakis (2-pyridylmethyl Ethylenediamine, diethylenetriamine, triethylenetetramine, N, N-bis (2-pyridylmethyl) amine, tris [2-aminoethyl] amine, 1,4,8,11-tetraazacyclotetradecane, and N, N, N ′ , N′-tetrakis (2-pyridylmethyl) ethylenediamine and wherein the optional second initiator is selected from peroxides, hydroperoxides or azo free radical initiators;
Thereby producing a block copolymer comprising the steps of:
Wherein the block copolymer comprises a polycarbonate block, wherein the polycarbonate block comprises 10% to 90% by weight of the block copolymer, and wherein the block copolymer comprises 1,000 to 70,000 Mw Comprising the steps of:

Embodiment 2: The method of embodiment 1, wherein R ¹ is selected from methyl, ethyl, and propyl, isopropyl.

Embodiment 3: The method according to any of embodiments 1-2, wherein X ¹ and X ² are each bromo, wherein R ¹ and R ² are each methyl.

Embodiment 4: The telechelic polycarbonate macroinitiator has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of 500-40,000, wherein the telechelic polycarbonate macroinitiator has a Mw of 1,000-70,000, and wherein Embodiment 4. The method according to any of embodiments 1-3, wherein X is selected from bromo and chloro.

  Embodiment 5: A method according to embodiment 4, wherein X is bromo.

Embodiment 6: The telechelic polycarbonate macroinitiator has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of 500-40,000, wherein the telechelic polycarbonate macroinitiator has a Mw of 1,000-70,000, 4. The method according to any one of 3.

  Embodiment 7: The telechelic polycarbonate macroinitiator has a Mn of 10,000 to 25,000 and the telechelic polycarbonate macroinitiator has a Mw of 20,000 to 50,000. The method according to any one of Forms 4 to 6.

Embodiment 8: A telechelic polycarbonate polymer having terminal hydroxyl groups has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate polymer has a Mn of 2,000-35,000, and wherein the telechelic polycarbonate polymer has a Mw of 3,400-70,000. Method.

  Embodiment 9: The telechelic polycarbonate polymer has a Mn of 5000 to 25,000, and wherein the telechelic polycarbonate macroinitiator has a Mw of 10,000 to 50,000. 9. The method according to any one of 8.

  Embodiment 10: A method according to any of embodiments 1 to 9, wherein 2 mol% to 3 mol% of the telechelic polycarbonate polymer is modified by reaction with an acid halide.

  Embodiment 11: A method according to any of embodiments 1 to 10, wherein the telechelic polycarbonate polymer having terminal hydroxyl groups has a Mw of 10,000 to 50,000.

  Embodiment 12: The method of any of embodiments 1 to 11, wherein the vinyl monomer is selected from methyl methacrylate, acrylate, styrene, and monoethylenically unsaturated nitrile monomer.

  Embodiment 13: The method according to any of Embodiments 1 to 12, wherein the vinyl monomer is polymethyl methacrylate.

  Embodiment 14: The method of embodiment 13, wherein the block copolymer comprises a polycarbonate block and a PMMA block.

  Embodiment 15: The method of embodiment 14, wherein the PMMA block is 10% to 90% by weight of the block copolymer composition.

  Embodiment 16: The method of embodiment 15, wherein the PMMA block is 40% to 90% by weight of the block copolymer composition.

Embodiment 17: The block copolymer has the formula:
Having the structure indicated by
Embodiment 17. The method of any of embodiments 1 to 16, wherein the block copolymer has a Mn of 500 to 40,000.

  Embodiment 18 The method of any of embodiments 1 to 17, wherein the block copolymer has a Mn of 10,000 to 25,000.

  Embodiment 19 The method of any of embodiments 1 to 18, wherein the block copolymer has a Mw of 10,000 to 60,000.

  Embodiment 20: A method according to any of embodiments 1 to 19, wherein the block copolymer has a Mw of 20,000 to 50,000.

  Embodiment 21: Embodiment wherein the block copolymer has a scratch width of 500 nm to 1,000 nm when tested under a load of 40 mN using a trihedral Berkovich diamond indenter with a front surface of 0.15 μm. The method in any one of 1-20.

  Embodiment 22: The block copolymer has a scratch width of 10 nm to 14 nm when tested under a load of 40 mN using a trihedral Berkovich diamond indenter with a front surface of 0.15 μm. The method according to any one of 21.

  Embodiment 23: The method according to any of embodiments 1-22, wherein the catalyst is Cu or a copper salt.

Embodiment 24: The above catalyst, CuBr, CuCl, CuCl _2, and are selected from CuBr _2, The method of any of embodiments 1-23.

  Embodiment 25 The catalyst ligand is 2,2′-bipyridine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, diethylenetriamine, triethylenetetramine, N, N-bis (2-pyridyl) Methyl) amine, tris [2-aminoethyl] amine, 1,4,8,11-tetraazacyclotetradecane, and 1,1,4,7,10,10-hexamethyltriethylenetetramine The method according to any one of Forms 1 to 24.

  Embodiment 26: A method according to any of embodiments 1 to 25, wherein said catalytic ligand is 2,2'-bipyridine.

  Embodiment 27: A method according to any of embodiments 1 to 26, wherein the optional second initiator is present and is an azo initiator.

  Embodiment 28: The method of embodiment 27, wherein the azo initiator is selected from 1,1'-azobis (cyclohexanecarbonitrile) and 2,2'-azobis (2-methylpropionitrile).

  Embodiment 29: A method according to embodiment 27 or embodiment 28, wherein the azo initiator is 2,2'-azobis (2-methylpropionitrile).

  Embodiment 30: Any of Embodiments 1-29, wherein the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, and catalyst ligand is from 25: 1: 1: 1 to 5000: 1: 100: 200. the method of.

  Embodiment 31: A method according to any of embodiments 1 to 30, wherein the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst and catalyst ligand is 200: 1: 1: 2.5.

  Embodiment 32: Embodiment 1 wherein the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand, and second initiator is about 200: 1: 0.05: 0.05: 0.1. 32. The method according to any one of -31.

Embodiment 33: R ¹ is selected from methyl and ethyl, wherein R ² is selected from methyl and ethyl, and each of X ¹ and X ² is bromo or chloro, wherein the catalyst is The method of any of embodiments 1-32, wherein the second initiator is azobisisobutyronitrile.

Embodiment 34: The method according to any of embodiments 1-32, comprising esterifying said hydroxyl group by reaction of a telechelic polycarbonate polymer with 2-bromoisobutyryl bromide, wherein Z ¹ and Z ² are formulas
Have
Wherein the second initiator is azobisisobutyronitrile and the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is 200: 1: 0.05: The method is 0.05: 0.1.

Embodiment 35: A copolymer comprising
A polycarbonate domain, wherein the polycarbonate domain has an Mw of at least 3,400, and wherein the polycarbonate domain is a polycarbonate domain comprising aromatic carbonate repeat units, a polyacrylate domain, and a vinyl monomer Wherein the polyacrylate domain is prepared by atom transfer radical polymerization of a vinyl monomer in the presence of a telechelic polycarbonate polymer, and wherein the polyacrylate domain is at least 2 mol% And a copolymer comprising a polyacrylate domain.

  Embodiment 36: The copolymer of embodiment 35, wherein the polycarbonate carbonate aromatic carbonate repeat unit comprises bisphenol A.

  Embodiment 37 The copolymer of any of embodiments 35 to 36, wherein the polycarbonate domain has a Mw of 10,000 to 50,000.

  Embodiment 38: The copolymer of any of embodiments 35-37, wherein the polyacrylate domain is PMMA.

  Embodiment 39: The copolymer of embodiment 38, wherein the PMMA is 10% to 90% by weight of the block copolymer composition.

  Embodiment 40: Embodiment 35 wherein the copolymer has a scratch depth of 500 nm to 1,000 nm when tested under a load of 40 mN using a trihedral Berkovich diamond indenter with a 0.15 μm front face. 40. Copolymer according to any of.

  Embodiment 41: The copolymer according to any of embodiments 35 to 40, wherein the copolymer is a block copolymer.

  Embodiment 42: The copolymer of any of embodiments 35-41, wherein the copolymer comprises a polycarbonate block and a polyacrylate block.

  Embodiment 43: The copolymer of embodiment 42, wherein the polycarbonate block is derived from a telechelic polycarbonate macroinitiator.

Embodiment 44: The copolymer of embodiment 43, wherein the telechelic polycarbonate macroinitiator has the formula:
Z ¹ -PC-Z ² ,
Have
Where PC is a polycarbonate polymer containing aromatic carbonate repeating units;
Where Z ¹ and Z ² are
Have
In the formula, ^{R 1} is hydrogen, C1-C6 alkyl, - is aryl, and aryl, wherein, ^{R 2} is C1-C6 alkyl, - - (C1-C6 alkyl) (C1-C6 alkyl) - A copolymer selected from aryl and aryl, wherein X is a halogen.

Embodiment 45: The copolymer of embodiment 43, wherein the telechelic polycarbonate macroinitiator is of the formula:
Having the structure indicated by
A copolymer wherein the telechelic polycarbonate macroinitiator has a Mn of 500-40,000, and wherein the telechelic polycarbonate macroinitiator has a Mw of 1,000-70,000.

  Embodiment 46: Embodiment wherein the telechelic polycarbonate macroinitiator has a Mn of 10,000 to 25,000 and the telechelic polycarbonate macroinitiator has a Mw of 20,000 to 50,000. The copolymer according to any one of 43 to 45.

Embodiment 47: The copolymer according to any of embodiments 41 to 46, wherein the block copolymer has the formula:
Having the structure indicated by
Wherein the block copolymer has a Mn of 500 to 40,000, and wherein the block copolymer has a Mw of 1,000 to 70,000.

  Embodiment 48: Any of Embodiments 41 through 47 wherein the block copolymer has a Mn of 10,000 to 25,000 and wherein the block copolymer has a Mw of 20,000 to 50,000. A copolymer according to any of the above.

  Embodiment 49: An article comprising the copolymer of any of embodiments 35-48.

  Embodiment 50: The article of embodiment 49, wherein the article is used in automotive applications.

  It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the detailed description and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the appended claims.

  The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments have structural elements that do not differ from the verbatim language of the claims, or they are not substantial with the verbal language of the claims. The inclusion of equivalent structural elements with differences is intended to be within the scope of the claims.

Claims (50)

A method for preparing a block copolymer comprising:
Providing a telechelic polycarbonate polymer having terminal hydroxyl groups, wherein the telechelic polycarbonate polymer has a weight average molecular weight of at least 3,400, and wherein the telechelic polycarbonate polymer is an aromatic carbonate repeating unit. Including steps, and
The hydroxyl group is represented by a telechelic polycarbonate polymer;
Esterifying by reaction with an acid halide having the structure represented by
Wherein R ¹ is selected from hydrogen, C1-C6 alkyl,-(C1-C6 alkyl) -aryl, and aryl, wherein R ² is C1-C6 alkyl,-(C1-C6 alkyl) -aryl, and Selected from aryl, and wherein each of X ¹ and X ² is halogen,
Thereby, the formula Z ¹ -PC-Z ² ,
To produce a telechelic polycarbonate macroinitiator having a structure represented by:
Wherein PC is a polycarbonate polymer containing aromatic carbonate repeating units, and Z ¹ and Z ² are
A step having
Reacting the polycarbonate macroinitiator with a vinyl monomer by atom transfer radical polymerization;
Wherein the atom transfer radical polymerization reaction comprises a catalyst, a catalyst ligand, a vinyl monomer, a polycarbonate macroinitiator, and an optional second initiator;
Wherein the catalyst is a transition metal or transition metal salt, and wherein the transition metal is selected from Ti, Mo, Re, Fe, Ru, Os, Rh, Co, Ni, Pd, and Cu;
Here, the ligand is 2,2′-bipyridine, 4,4′-di (5-nonyl) -2,2′-bipyridine, N, N, N ′, N′-tetramethylethylenediamine, N-propyl ( 2-pyridyl) methanimine, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4,4 ′, 4 ″ -tris (5-nonyl) -2,2 ′: 6 ′, 2 ″ -terpyridine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N-bis (2-pyridylmethyl) octylamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine , Tris [2- (dimethylamino) ethyl] amine, tris [(2-pyridyl) methyl] amine, 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane, N, N , N ′, N′-tetrakis (2-pyridylmethyl) Tylenediamine, diethylenetriamine, triethylenetetramine, N, N-bis (2-pyridylmethyl) amine, tris [2-aminoethyl] amine, 1,4,8,11-tetraazacyclotetradecane, and N, N, N Selected from ', N'-tetrakis (2-pyridylmethyl) ethylenediamine and wherein the optional second initiator is selected from a peroxide, hydroperoxide or azo free radical initiator;
Thereby producing a block copolymer,
Wherein the block copolymer comprises a polycarbonate block, wherein the polycarbonate block comprises from 10% to 90% by weight of the block copolymer, and wherein the block copolymer comprises from 1,000 to 70,000 Mw A step comprising:
Including the method. The method of claim 1, wherein R ¹ is selected from methyl, ethyl, and propyl, isopropyl. Each X ¹ and ^{X 2,} bromo, wherein a ^{R 1} and ^{R 2} are each methyl, A method according to any one of claims 1-2. The telechelic polycarbonate macroinitiator has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of 500-40,000, wherein the telechelic polycarbonate macroinitiator has a Mw of 1,000-70,000, and wherein 4. A process according to any one of claims 1 to 3, wherein X is selected from bromo and chloro.   The method of claim 4, wherein X is bromo. The telechelic polycarbonate macroinitiator has the formula:
Having the structure indicated by
Wherein the telechelic polycarbonate macroinitiator has a Mn of 500-40,000, and wherein the telechelic polycarbonate macroinitiator has a Mw of 1,000-70,000. The method of any one of -3.   7. The telechelic polycarbonate macroinitiator has a Mn of 10,000 to 25,000, wherein the telechelic polycarbonate macroinitiator has a Mw of 20,000 to 50,000. The method of any one of these. The telechelic polycarbonate polymer having terminal hydroxyl groups has the formula:
Having the structure indicated by
2. The telechelic polycarbonate polymer according to claim 1, wherein the telechelic polycarbonate polymer has a Mn of 2,000 to 35,000, and wherein the telechelic polycarbonate polymer has a Mw of 3,400 to 70,000. Method.   9. The telechelic polycarbonate polymer of claim 1-8, wherein the telechelic polycarbonate polymer has a Mn of 5,000 to 25,000, and wherein the telechelic polycarbonate macroinitiator has a Mw of 10,000 to 50,000. The method according to any one of the above.   The method according to any one of claims 1 to 9, wherein 2 mol% to 3 mol% of the telechelic polycarbonate polymer is modified by reaction with an acid halide.   The method according to any one of claims 1 to 10, wherein the telechelic polycarbonate polymer having terminal hydroxyl groups has a Mw of 10,000 to 50,000.   12. A method according to any one of the preceding claims, wherein the vinyl monomer is selected from methyl methacrylate, acrylate, styrene, and monoethylenically unsaturated nitrile monomer.   The method according to claim 1, wherein the vinyl monomer is polymethyl methacrylate.   The method of claim 13, wherein the block copolymer comprises a polycarbonate block and a PMMA block.   15. The method of claim 14, wherein the PMMA block is 10% to 90% by weight of the block copolymer composition.   16. The method of claim 15, wherein the PMMA block is 40% to 90% by weight of the block copolymer composition. The block copolymer has the formula:
Having the structure indicated by
17. A method according to any one of claims 1 to 16, wherein the block copolymer has a Mn of 500 to 40,000.   18. A method according to any one of claims 1 to 17, wherein the block copolymer has a Mn of 10,000 to 25,000.   19. A method according to any one of the preceding claims, wherein the block copolymer has a Mw of 10,000-60,000.   20. A method according to any one of the preceding claims, wherein the block copolymer has a Mw of 20,000 to 50,000.   21. The block copolymer of claim 1-20, wherein the block copolymer has a scratch depth of 500 nm to 1,000 nm when tested under a load of 40 mN using a three-sided Berkovich diamond indenter having a front surface of 0.15 μm. The method according to any one of the above.   22. The block copolymer according to any one of claims 1 to 21, wherein the block copolymer has a scratch width of 10 nm to 14 nm when tested under a load of 40 mN using a trihedral Berkovich diamond indenter having a front surface of 0.15 μm. 2. The method according to item 1.   The method according to any one of claims 1 to 22, wherein the catalyst is Cu or a copper salt. It said catalyst, CuBr, CuCl, CuCl _2, and are selected from CuBr _2, The method according to any one of claims 1 to 23.   The catalyst ligand is 2,2′-bipyridine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, diethylenetriamine, triethylenetetramine, N, N-bis (2-pyridylmethyl) amine, 25. Selected from tris [2-aminoethyl] amine, 1,4,8,11-tetraazacyclotetradecane, and 1,1,4,7,10,10-hexamethyltriethylenetetramine. The method of any one of these.   26. A method according to any one of claims 1 to 25, wherein the catalytic ligand is 2,2'-bipyridine.   27. A method according to any one of claims 1 to 26, wherein the optional second initiator is present and is an azo initiator.   28. The process of claim 27, wherein the azo initiator is selected from 1,1'-azobis (cyclohexanecarbonitrile) and 2,2'-azobis (2-methylpropionitrile).   29. A process according to claim 27 or claim 28, wherein the azo initiator is 2,2'-azobis (2-methylpropionitrile).   30. A process according to any one of claims 1 to 29, wherein the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst and catalyst ligand is from 25: 1: 1: 1 to 5000: 1: 100: 200. .   31. The method of any one of claims 1-30, wherein the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, and catalyst ligand is about 200: 1: 1: 2.5.   32. Any of claims 1-31 wherein the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand, and second initiator is about 200: 1: 0.05: 0.05: 0.1. The method according to claim 1. R ¹ is selected from methyl and ethyl, wherein R ² is selected from methyl and ethyl, and each of X ¹ and X ² is bromo or chloro, wherein the catalyst is a copper salt 35. The method of any one of claims 1-32, wherein and wherein the second initiator is azobisisobutyronitrile. A method according to any one of claims 1 to 32, includes the step of esterifying the hydroxyl groups by reaction with a telechelic polycarbonate polymer and 2-bromo isobutyryl bromide, wherein Z ¹ And Z ² is the formula,
Have
Wherein the second initiator is azobisisobutyronitrile and the molar ratio of vinyl monomer, polycarbonate macroinitiator, catalyst, catalyst ligand and second initiator is 200: 1: 0.05: The method is 0.05: 0.1. A copolymer comprising:
A polycarbonate domain, wherein the polycarbonate domain has an Mw of at least 3,400, and wherein the polycarbonate domain comprises an aromatic carbonate repeating unit;
A polyacrylate domain, containing repeating units derived from vinyl monomers;
Wherein the polyacrylate domain is prepared by atom transfer radical polymerization of vinyl monomers in the presence of a telechelic polycarbonate polymer, and wherein the polyacrylate domain comprises a polyacrylate domain comprising at least 2 mol% copolymer; Including copolymers.   36. The copolymer of claim 35, wherein the polycarbonate domain aromatic carbonate repeat unit comprises bisphenol A.   37. The copolymer of any one of claims 35 to 36, wherein the polycarbonate domain has a Mw of 10,000 to 50,000.   38. The copolymer of any one of claims 35 to 37, wherein the polyacrylate domain is PMMA.   39. The copolymer of claim 38, wherein the PMMA is 10% to 90% by weight of the block copolymer composition.   40. Any of claims 35 to 39, wherein the copolymer has a scratch depth of 500 nm to 1,000 nm when tested under a load of 40 mN using a trihedral Berkovich diamond indenter having a 0.15 μm front face. A copolymer according to claim 1.   41. The copolymer according to any one of claims 35 to 40, wherein the copolymer is a block copolymer.   42. The copolymer of any one of claims 35 to 41, wherein the copolymer comprises a polycarbonate block and a polyacrylate block.   43. The copolymer of claim 42, wherein the polycarbonate block is derived from a telechelic polycarbonate macroinitiator. 44. The copolymer of claim 43, comprising:
The telechelic polycarbonate macroinitiator has the formula:
Z ¹ -PC-Z ² ,
Have
Where PC is a polycarbonate polymer containing aromatic carbonate repeating units;
Where Z ¹ and Z ² are
Have
Wherein R ¹ is selected from hydrogen, C1-C6 alkyl,-(C1-C6 alkyl) -aryl, and aryl;
Wherein R ² is selected from C 1 -C 6 alkyl, — (C 1 -C 6 alkyl) -aryl, and aryl, and wherein X is a halogen,
Copolymer. The telechelic polycarbonate macroinitiator is a formula,
Having the structure indicated by
44. The telechelic polycarbonate macroinitiator has a Mn of 500-40,000, and wherein the telechelic polycarbonate macroinitiator has a Mw of 1,000-70,000. Copolymer.   46. The telechelic polycarbonate macroinitiator has a Mn of 10,000 to 25,000 and the telechelic polycarbonate macroinitiator has a Mw of 20,000 to 50,000. The copolymer according to any one of the above. The block copolymer has the formula:
Having the structure indicated by
47. Any one of claims 41 to 46, wherein the block copolymer has a Mn of 500 to 40,000, and wherein the block copolymer has a Mw of 1,000 to 70,000. Copolymers described in 1.   48. The method of any one of claims 41 to 47, wherein the block copolymer has a Mn of 10,000 to 25,000, and wherein the block copolymer has a Mw of 20,000 to 50,000. The copolymer described.   49. An article comprising the copolymer of any one of claims 35-48.   50. The article of claim 49, wherein the article is used in automotive applications.